Research progress on the growth behavior of hydrates in water-in-oil emulsion systems

doi:10.16085/j.issn.1000-6613.2022-1736

Abstract

Abstract:

The variation of hydrate growth behaviors can affect the growth rate and formation amount of hydrates in water-oil emulsions, posing challenges to the safe operation of multiphase pipelines and the development of flow assurance strategies. In this work, the experimental methods for hydrate formation and the quantitative indexes of hydrate growth rate are systematically reviewed. The influence of key factors (e.g., composition of oil phase and water cut) on hydrate growth behavior is summarized. In addition, the research progress on the growth mechanisms and the quantitative models of hydrate formation are deeply analyzed. Overall, the experimental methodology and quantitative indexes of hydrate growth have been well-developed, and a deeper understanding of the influencing factors and growth mechanism has been gained. In future studies, the hydrate growth behaviors under multi-component complex systems should be further explored. The understanding of hydrate shell structure and growth mechanism in water-in-oil emulsions should be deepened from the microscopic perspective. Based on all these studies, the hydrate growth rate model for actual multiphase pipelines could be established.

Key words: hydrate, mass transfer, kinetics, flow assurance, water-in-oil emulsion, growth behavior

摘要：

油包水乳状液中水合物生长行为的差异会影响水合物的生长速率和生成量，为多相管道的安全运行和流动保障策略的制定带来挑战。本文结合国内外关于油包水乳状液中水合物生成行为的实验及理论研究成果，系统阐述了水合物生成实验研究方法及水合物生长过程常用量化指标，总结了油水体系中油相组成、含水率等因素对水合物生长行为的影响规律，分析了油包水乳状液中水合物的生长机理和量化模型的研究进展。文章指出，油包水乳状液中水合物生成方法和量化指标已较为完善，对影响因素和生长机理的认识正日趋深入。未来应进一步探明多组分复杂体系下的水合物生长动力学行为，并从微观角度深入对油水体系中水合物壳体结构及生长机理的理解，最终建立适用于实际多相管道的水合物生长速率模型。

关键词: 水合物, 传质, 动力学, 流动保障, 油包水乳状液, 生长行为

CLC Number:

TE89

WANG Wei, ZHANG Dongxu, LI Zunzhao, WANG Xiaolin, HUANG Qiyu. Research progress on the growth behavior of hydrates in water-in-oil emulsion systems[J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1155-1166.

王唯, 张东旭, 李遵照, 王晓霖, 黄启玉. 油包水乳状液体系中水合物生长行为研究进展[J]. 化工进展, 2023, 42(3): 1155-1166.

Figures/Tables 10

生成方法	操作过程	方法特性
恒温恒压法	控制多相体系在短时间内降温和升压，直至达到三相平衡条件下的某一状态，而后维持体系稳定直至水合物生成^[8]	可使不同组成的体系中水合物开始生长时的温度和压力相同，便于比较水合物生长速率和生成量
恒容降温法	将多相体系升压至高压状态，而后关闭进气阀进行降温，使体系在恒容条件下逐渐降温至水合物生成^[16]	应用范围广，操作相对简单，但由于不同组成的体系中水合物的诱导期存在差异，所以水合物开始生长时的初始压力和温度很难保持一致，因而不利于水合物生长速率的比较
恒压降温法	将多相体系升压至高压状态后降温直至水合物生成，降温过程中调节装置进气量以维持水合物生成前体系压力恒定^{[17, 18]}	减弱了不同组成的体系中水合物生长开始时温度、压力不同对水合物生长速率的干扰，有利于水合物生长速率的比较
恒温升压法	将多相体系降温达到恒定过冷度，而后以恒定速率升压直至水合物生成^{[17, 19]}	操作相对简单，但与海底管道内温度、压力变化趋势不同
诱导转化法	将冰粒放置于水合物生成介质中促使水合物颗粒快速形成^{[20, 21]}	水合物生成速度快，多用于研究水合物颗粒间黏附力变化规律，但操作相对复杂

量化描述方法	所需参数/计算公式	研究者（研究装置）
参数变化速率	温度或压力	Zhang等^[22]（反应釜）
气体消耗量	$n t = P i V g Z i R T i + n d, i - P t V g Z t R T t + n d, t$	Wang等^[17]、Azam等^[32]、Lyu等^[33]（反应釜） Shi等^[24]、Lyu等^[34]、Zhou等^[35]（高压环道） Mu等^[36]（摇摆反应装置）
初始气体消耗速率	$R i n i = n i n i / t i n i$	Turner等^[7]、Ning等^[31]、Akhfash等^[37]（反应釜）
90%生成量平均速率	$R a, 90 = n 90 / t 90$	Liu等^[27]（反应釜）
水相转化率	$C W H = N h y d n t / n w a t e r × 100 %$	Zi等^[28]（反应釜） Davies等^[38]（高压环道）
水合物体积分数	$ψ h = n t M g + N h y d n t M w / ρ H V L + n t M g + N h y d n t M w / ρ H - N h y d n t M w / ρ w$	柳扬^[39]（高压环道） Qin等^[29]（高压流变仪） Akhfash等^[37]、Shi等^[40]（反应釜）
壳体生长速率	水合物壳体比表面积和时间	Song等^[30]、Guo等^[41]（常压反应釜）

量化描述方法	所需参数/计算公式	研究者（研究装置）
参数变化速率	温度或压力	Zhang等^[22]（反应釜）
气体消耗量	$n t = P i V g Z i R T i + n d, i - P t V g Z t R T t + n d, t$	Wang等^[17]、Azam等^[32]、Lyu等^[33]（反应釜） Shi等^[24]、Lyu等^[34]、Zhou等^[35]（高压环道） Mu等^[36]（摇摆反应装置）
初始气体消耗速率	$R i n i = n i n i / t i n i$	Turner等^[7]、Ning等^[31]、Akhfash等^[37]（反应釜）
90%生成量平均速率	$R a, 90 = n 90 / t 90$	Liu等^[27]（反应釜）
水相转化率	$C W H = N h y d n t / n w a t e r × 100 %$	Zi等^[28]（反应釜） Davies等^[38]（高压环道）
水合物体积分数	$ψ h = n t M g + N h y d n t M w / ρ H V L + n t M g + N h y d n t M w / ρ H - N h y d n t M w / ρ w$	柳扬^[39]（高压环道） Qin等^[29]（高压流变仪） Akhfash等^[37]、Shi等^[40]（反应釜）
壳体生长速率	水合物壳体比表面积和时间	Song等^[30]、Guo等^[41]（常压反应釜）

原油重质组分	研究者	生成方法	速率表征方法	主要研究结论
蜡	Chen等^[16]（2018）	恒容降温法	水合物体积分数	蜡降低了水合物平均生长速率
	周诗岽等^[45]（2018）	恒温恒压法	气体消耗量	水合物生成量随含蜡量的升高而增加
	Wang等^[17]（2019）	恒压降温法和恒温升压法	气体消耗量	蜡可增加水合物生成量
	Liu等^[46]（2019）	恒容降温法	气体消耗量	蜡促进了水合物初始生长过程
	Song等^[30]（2020）	诱导转化法	壳体平均生长速率	蜡降低了水合物壳体生长速率
	Liu等^[47]（2022）	恒容降温法	气体消耗量	蜡晶析出减少了水合物生成量
沥青质	Zi等^[28]（2021）	恒容降温法	水相转化率	模拟沥青质的加入降低了水合物生成量
	Zhang等^[48]（2021）	恒压降温法和恒温升压法	气体消耗量	沥青质提高了水合物初始生长速率但降低了最终生成量
	Ning等^[31]（2021）	恒容降温法	初始耗气速率	沥青质降低了水合物初始生长速率
	Prasad等^[49]（2021）	恒温恒压法	气体消耗量	低含量沥青质增加了水合物生长过程中的气体消耗量
	Song等^[50]（2022）	诱导转化法	壳体平均生长速率	水合物壳体生长速率随沥青质含量增加而逐渐降低
胶质	Zhang等^[22]（2020）	恒压降温法	参数变化速率	胶质降低了水合物生长速率
蜡+沥青质	Zhang等^[18]（2021）	恒压降温法	气体消耗量	组分间协同作用增强了沥青质对水合物生长的抑制效果

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