蜡晶析出对CO2水合物相平衡及诱导特性的影响

doi:10.16085/j.issn.1000-6613.2020-1086

摘要/Abstract

摘要：

为了探明蜡晶析出对水合物生成相平衡特性及成核特性的影响，本文选用2^#工业白油与60^#昆仑石蜡的混合溶液来模拟含蜡体系，利用高压可视化搅拌釜开展含蜡体系水合物生成实验，结合水合物生成过程中的可视化图像，研究不同蜡晶浓度对水合物生成相平衡曲线、水合物成核诱导时间、诱导时间变化率的影响规律及蜡晶析出对水合物生成机理的影响。结果表明：①随着蜡晶浓度的增加，水合物生成相平衡条件逐渐降低，相平衡曲线较无蜡体系向右偏移，且蜡晶浓度越大，偏移趋势越明显，在温度281.5K时，3.5%（质量分数）的蜡含量比无蜡体系的相平衡压力降低6.5%；②通过分析不同蜡晶浓度对水合物成核诱导时间的影响发现，蜡晶析出加快了水合物结晶，缩短了水合物成核诱导时间，且蜡晶浓度越大，诱导时间缩短越明显；③通过探究不同蜡晶浓度对水合物成核诱导能力的影响发现，随着蜡晶浓度的增加，蜡晶析出对水合物诱导成核的促进能力总体呈现先增大后减小的趋势，即蜡晶对水合物的促进能力不是无限增大的，会随蜡晶浓度的增加逐渐减弱；④通过分析蜡晶析出对水合物生成速率及生成位置的影响发现，当体系达到水合物生成条件时，反应釜中心部分的水合物会先于气液表面及釜壁生成。本文研究成果有助于深海油气开采的应用发展，同时为更好研究蜡晶与水合物耦合特性提供可靠的pVT数据。

关键词: 水合物, 相平衡曲线, 诱导时间, 诱导时间变化率

Abstract:

In order to prove the influence of wax crystal precipitation on the phase equilibrium and nucleation characteristics of hydrate formation, this paper selected a mixed solution of 2^# industrial white oil and 60^# Kunlun paraffin to simulate the wax-containing system. Using a high-pressure visual stirred tank and combining with the visualization images during the hydrate formation process, we studied the influence of different wax concentrations on the hydrate formation phase equilibrium curve, hydrate nucleation induction time, and induction time change rate, and explored the effects of wax crystal precipitation on hydrate generation mechanism. The results show that as the concentration of wax crystals increases, the phase equilibrium conditions for hydrate formation gradually decrease, and the phase equilibrium curve shifts to the right compared to the wax-free system; the greater the wax crystal concentration, the more obvious the tendency to shift; at 281.5K and the wax content of 3.5%(mass fraction), the phase equilibrium pressure decreases by 6.5% compared with that of the wax-free system. By analyzing the effect of different wax crystal concentrations on the hydrate nucleation induction time, it is found that the precipitation of wax crystals accelerates the hydrate crystallization, shortens the hydrate nucleation induction time, and the greater the wax crystals concentration, the more obvious the shortening of the induction time. By exploring the effect of different wax crystal concentrations on the hydrate nucleation-inducing ability, it is found that with the increase of wax crystal concentration, the promotion ability of wax crystal precipitation to hydrate-induced nucleation increases at first and then decreases. By analyzing the influence of wax precipitation on the hydrate formation rate and location, it is found that when the system reaches the hydrate formation condition, the hydrate in the center of the reaction reactor is generated earlier than at the gas-liquid surface and the kettle wall. The research results are helpful to the application and development of deep sea-oil and gas exploitation, and provide reliable pVT data for studying the coupling characteristics of wax crystal and hydrate.

Key words: hydrate, phase equilibrium curve, induction time, rate of change of induction time

中图分类号:

TE832

胡倩, 周诗岽, 郭宇, 张雪艳, 王娇娇, 王国栋, 姬浩洋. 蜡晶析出对CO₂水合物相平衡及诱导特性的影响[J]. 化工进展, 2021, 40(5): 2452-2460.

HU Qian, ZHOU Shidong, GUO Yu, ZHANG Xueyan, WANG Jiaojiao, WANG Guodong, JI Haoyang. Influence of wax crystal precipitation on the phase equilibrium and induction characteristics of CO₂hydrate[J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2452-2460.

图/表 12

参考文献 27

1	潘振, 王喆, 商丽艳, 等. 油水乳液体系中甲烷水合物生成研究进展[J]. 化工进展, 2017, 36(12): 4392-4402.
	PAN Zhen, WANG Zhe, SHANG Liyan, et al. Research progress on methane hydrate formation in oil and water emulsion[J]. Chemical Industry and Engineering Progress, 2017, 36(12): 4392-4402.
2	周诗岽, 于雪薇, 江坤, 等. 蜡晶析出对天然气水合物生成动力学特性的影响[J]. 天然气工业, 2018, 38(3): 103-109.
	ZHOU Shidong, YU Xuewei, JIANG Kun, et al. Effect of wax crystal precipitation on the kinetic characteristics of hydrate formation[J]. Natural Gas Industry, 2018, 38(3): 103-109.
3	史博会, 于一帆, 胡元甲, 等. 蜡晶析出沉积与水合物结晶生成耦合热力学与动力学研究进展[J]. 科学通报, 2018, 63(3): 283-300.
	SHI Bohui, YU Yifan, HU Yuanjia, et al. Advances in coupling thermodynamics and kinetics studies of wax precipitation-deposition and hydrate nucleation-formation[J].Chinese Science Bulletin, 2018, 63(3): 283-300.
4	仇朝军, 刘旭文, 卢新鹏, 等. 渤海某高含二氧化碳油气田海管腐蚀研究[J]. 全面腐蚀控制, 2012, 26(4): 22-25.
	QIU Zhaojun, LIU Xuwen, LU Xinpeng, et al. The corrosion research which contained higher carbon dioxide of Bohai oil field[J]. Total Corrosion Control, 2012, 26(4): 22-25.
5	万里平, 孟英峰, 梁发书. 油气田开发中的二氧化碳腐蚀及影响因素[J]. 全面腐蚀控制, 2003, 17(2): 14-17.
	WAN Liping, MENG Yingfeng, LIANG Fashu. Carbon dioxide corrosion and its influence factors in oil/gas field exploitation[J].Total Corrosion Control, 2003, 17(2): 14-17.
6	ZHANG K. Study of the influence of liquid hydrocarbon existence and wax precipitation on hydrate formation in subsea pipeline (in Chinese)[D]. Qingdao: ChinaUniversity of Petroleum, 2011: 32-58.
7	JI H Y. Thermodynamic modelling of wax and integrated wax-hydrate[D]. Edinburgh:Heriot-Watt University, 2004.
8	GAO S Q. Investigation of interactions between gas hydrates and several other flow assurance elements[J]. Energy & Fuels, 2008, 22(5): 3150-3153.
9	MAHABADIAN M A, CHAPOY A, BURGASS R, et al. Mutual effects of paraffin waxes and clathrate hydrates:a multiphase integrated thermodynamic model and experimental measurements[J]. Fluid Phase Equilibria, 2016, 427: 438-459.
10	DE OLIVEIRA M C K, TEIXEIRA A, VIEIRA L C, et al. Flow assurance study for waxy crude oils[J]. Energy & Fuels, 2012, 26(5): 2688-2695.
11	MOHAMMADI A H, JI H,BURGASS R W, et al.Gas hydrates in oil systems[C]//Proceedings of SPE Europec/EAGE Annual Conference and Exhibition. Vienna: Society of Petroleum Engineers, 2006.
12	TABATABAEI A R, DANESH A, TOHIDI B, et al. A consistent thermodynamic model for predicting combined wax-hydrate in petroleum reservoir fluids[J]. Annals of the New York Academy of Sciences, 2006, 912(1): 392-402.
13	史博会, 雍宇, 柳杨, 等. 含蜡和防聚剂体系天然气水合物浆液生成及流动特性[J]. 化工进展, 2018, 37(6): 2182-2191.
	SHI Bohui, YONG Yu, LIU Yang, et al. Characteristics of natural gas hydrate slurry formation and flow in systems with wax and anti-agglomerates[J].Chemical Industry and Engineering Progress, 2018, 37(6): 2182-2191.
14	SLOAN E D, FLEYFEL F.A molecular mechanism for gas hydrate nucleation from ice[J]. AIChE Journal, 1991, 37(9): 1281-1292.
15	雍宇, 史博会, 丁麟, 等. 水合物生成诱导期研究进展[J]. 化工进展, 2018, 37(2): 505-516.
	YONG Yu, SHI Bohui, DING Lin, et al. Research progress of hydrate formation induction time[J]. Chemical Industry and Engineering Progress, 2018, 37(2): 505-516.
16	SHI B H, CHAI S, LIU Y, et al. Experimental study on natural gas hydrates nucleation induction time in the presence of wax crystal[C]//Proceedings of 9th International Conference of Gas Hydrates. Denver, 2017.
17	SONG X F, XIN F, YAN H C, et al. Intensification and kinetics of methane hydrate formation under heat removal by phase change of n-tetradecane[J]. AIChE Journal, 2015, 61(10): 3441-3450.
18	孙志高, 石磊, 樊栓狮, 等. 气体水合物相平衡测定方法研究[J]. 石油与天然气化工, 2001, 30(4): 164-166, 157.
	SUN Zhigao, SHI Lei, FAN Shuanshi, et al. Study of the measuring methods of gas hydrate phase equilibrium[J]. Chemical Engineering of Oil & Gas, 2001, 30(4): 164-166, 157.
19	梅东海, 廖健, 王璐琨, 等. 气体水合物相平衡生成条件的测定及预测[J]. 高校化学工程学报, 1997, 11(3): 225-230.
	MEI Donghai, LIAO Jian, WANG Lukun, et al. Measurement and prediction of the equilibrium formation conditions for gas hydrates[J]. Journal of Chemical Engineering of Chinese Universities, 1997, 11(3): 225-230.
20	NATARAJAN V, BISHNOI P R, KALOGERAKIS N. Induction phenomena in gas hydrate nucleation[J]. ChemEngSci, 1994, 49(13): 2075-2087.
21	潘云仙, 刘道平, 黄文件, 等. 气体水合物形成时的诱导时间定义辨析[J]. 上海理工大学学报, 2006, 28(1): 1-4, 22.
	PAN Yunxian, LIU Daoping, HUANG Wenjian, et al.Dischmination of the definition of induction time in gas hydrate formation[J]. Journal of University of Shanghai for Science and Technology, 2006, 28(1): 1-4, 22.
22	潘云仙, 刘道平, 黄文件, 等. 气体水合物形成的诱导时间及其影响因素[J]. 天然气地球科学, 2005, 16(2): 255- 260.
	PAN Yunxian, LIU Daoping, HUANG Wenjian, et al.The induction time and the affected factors in gas hydrate formation[J]. Natural Gas Geoscience, 2005, 16(2): 255-260.
23	王亚东, 赵建忠, 高强, 等. 石英砂介质中甲烷水合物生成过程和相平衡的实验研究[J].石油与天然气化工, 2018, 47(6): 44-49.
	WANG Yadong, ZHAO Jianzhong, GAO Qiang, et al. Experimental study on the formation and phase equilibria of methane hydrate in quartz sand media[J]. Chemical Engineering of Oil & Gas, 2018, 47(6): 44-49.
24	KASHCHIEV D, FIROOZABADI A. Induction time in crystallization of gas hydrates[J]. Journal of Crystal Growth, 2003, 250: 499-515.
25	寇杰, 张楠, 李云, 等. 海底混输管道析蜡对水合物生成的影响[J]. 中国石油大学学报(自然科学版), 2016, 40(4): 171-175.
	KOU Jie, ZHANG Nan, LI Yun, et al.Effect of wax formation on hydrate precipitation in subsea multiphase pipeline[J]. Journal of China University of Petroleum(Edition of Natural Science), 2016, 40(4): 171-175.
26	WANG P, WANG W, GONG J, et al.Effects of the dispersed phase on oil/water wax deposition[J]. Journal of Energy Resources Technology, 2013, 135(4): 042902.
27	MA Q L, WANG W, LIU Y, et al. Wax adsorption at paraffin oil-water interface stabilized by Span80[J]. Colloids & Surfaces A: Physicochemical & Engineering Aspects, 2017, 518: 73-79.

材料名称	纯度/%	提供厂家
蒸馏水		实验室自制
CO₂	99.9	常州市武进区华阳气体有限公司
2^#工业白油	99	广东中海南联能源有限公司
60^#昆仑石蜡	99	中国石油天然气股份有限公司

材料名称	纯度/%	提供厂家
蒸馏水		实验室自制
CO₂	99.9	常州市武进区华阳气体有限公司
2^#工业白油	99	广东中海南联能源有限公司
60^#昆仑石蜡	99	中国石油天然气股份有限公司

实验体系	实验材料		加液量/mL	加水量/mL	搅拌速率/r·min^-1
实验体系	2^#工业白油（质量分数）/%	60^#昆仑石蜡（质量分数）/%	加液量/mL	加水量/mL	搅拌速率/r·min^-1
体系1	100	0	70	50	600
体系2	98.5	1.5	70	50	600
体系3	97.5	2.5	70	50	600
体系4	96.5	3.5	70	50	600

实验体系	实验材料		加液量/mL	加水量/mL	搅拌速率/r·min^-1
实验体系	2^#工业白油（质量分数）/%	60^#昆仑石蜡（质量分数）/%	加液量/mL	加水量/mL	搅拌速率/r·min^-1
体系1	100	0	70	50	600
体系2	98.5	1.5	70	50	600
体系3	97.5	2.5	70	50	600
体系4	96.5	3.5	70	50	600

实验体系	实验材料		初始压力p₀/MPa	加液量/mL	加水量/mL	搅拌速率/r·min^-1
实验体系	2^#工业白油（质量分数）/%	60^#昆仑石蜡（质量分数）/%	初始压力p₀/MPa	加液量/mL	加水量/mL	搅拌速率/r·min^-1
体系1	100	0	3.9	70	50	600
体系1	100	0	4.6	70	50	600
体系2	98.5	1.5	3.9	70	50	600
体系2	98.5	1.5	4.6	70	50	600
体系3	97.5	2.5	3.9	70	50	600
体系3	97.5	2.5	4.6	70	50	600
体系4	96.5	3.5	3.9	70	50	600
体系4	96.5	3.5	4.6	70	50	600

蜡晶析出对CO₂水合物相平衡及诱导特性的影响

Influence of wax crystal precipitation on the phase equilibrium and induction characteristics of CO₂hydrate

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参考文献 27

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初始压力p₀	蜡晶质量分数
初始压力p₀	0~1.5%	0~2.5%	0~3.5%
3.9MPa	6.75%	15.81%	18.97%
4.6MPa	2.45%	11.76%	14.71%

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