间歇流条件下二氧化碳水合物生成诱导特性

doi:10.16085/j.issn.1000-6613.2019-1227

摘要/Abstract

摘要：

为明确二氧化碳水合物在间歇流条件下诱导时间的变化规律，本文在高压水合物循环实验环路上进行了气团流及段塞流体系下的二氧化碳水合物生成实验，结果表明：气团流范围内诱导时间随流量增大而减小，而段塞流范围内诱导时间随流量增大而增大。分析产生该现象的原因为，气团流时，制约水合物成核的主要因素是气液接触面积，而在段塞流时，制约水合物成核的主要因素已变为温降速率下降导致的成核驱动力下降。同时，结合间歇流参数模型与气体水合物诱导时间模型，建立了流型对诱导时间影响的预测模型，模型计算值与实验值具有较好的吻合性，相对误差均在10%以内。

关键词: 水合物, 诱导时间, 气团流, 段塞流, 模型

Abstract:

In order to clarify the variation of the induction time for carbon dioxide hydrate under intermittent flow conditions, experiments on the formation of CO₂ hydrate under air mass flow and slug flow system were carried out in the high-pressure visible hydrate loop. The results showed that the induction time decreased as the flow rate increased under the air mass flow. However, the induction time increased as the flow rate increased under the slug flow. The reason for this phenomenon was that the gas-liquid contact area was the main factor restricting hydrate nucleation in air mass flow, while in slug flow, the main factor had become the decrease of nucleation driving force caused by the decrease of temperature drop rate. Meanwhile, the prediction model of the influence of flow pattern on induction time was established with the intermittent flow parameter model and the gas hydrate induction time model, the calculated value of which was in good agreement with the experimental data , and the relative error was less than 10%.

Key words: hydrate, induction time, air mass flow, slug flow, model

中图分类号:

TE832

何骋远,周诗岽,秦天成,张文文,吕晓方,王树立,姬浩洋. 间歇流条件下二氧化碳水合物生成诱导特性[J]. 化工进展, 2020, 39(4): 1348-1356.

Chengyuan HE,Shidong ZHOU,Tiancheng QIN,Wenwen ZHANG,Xiaofang LÜ,Shuli WANG,Haoyang JI. Induction characteristics of carbon dioxide hydrate formation under intermittent flow[J]. Chemical Industry and Engineering Progress, 2020, 39(4): 1348-1356.

图/表 15

图1 高压可视实验环路示意图1—气瓶；2—气体增压泵；3—缓冲罐；4—质量流量计；5—储液罐；6—涡轮流量计；7—液体增压泵；8—质量流量计；9、10—观测口；11—循环泵；12—反应釜；V1、V5—压力调节阀；V2～V4、V7、V9、V14～V16—针型阀；V6、V8、V10—止回阀；V11～V13、V18—高压球阀；V15—安全阀；PR1-5—压力传感器；TR1～TR5—温度传感器；PDR1、PDR2—压差变送器

表1 各工况实验参数

工况	压力/MPa	温度/℃	气液体积比	流量/L?min^-1	流型
1	3	0.5	7∶33	1.68	气团流
2	3	0.5	7∶33	3.36	气团流
3	3	0.5	7∶33	8.40	气团流
4	3	0.5	7∶33	13.44	段塞流
5	3	0.5	7∶33	16.80	段塞流
6	3	0.5	7∶33	26.88	段塞流

图2 典型的温度与压力曲线（气团流）

图3 水合物生成前管内流型

图4 诱导时间结束时刻管内实验现象

图5 气团流下诱导时间及过冷度与流量的关系

图6 段塞流下诱导时间及过冷度与流量的关系

图7 不同流量下流体的温度对比

表2 各工况诱导时间模型参数

工况	$z$	$n *$	A/×10³⁵m^-3·s^-1	G/m^-2·s^-1	J/m^-3·s^-1
1	0.00832	340	8.3081	22.1351	2411.916
2	0.00799	353	8.0842	21.0259	2853.709
3	0.00664	423	7.1462	16.7883	3734.732
4	0.00426	653	5.2879	9.9271	13277.710
5	0.00440	635	5.4180	10.3682	6783.020
6	0.00753	372	7.7604	19.4411	6380.770

表2 各工况诱导时间模型参数

工况	$z$	$n *$	A/×10³⁵m^-3·s^-1	G/m^-2·s^-1	J/m^-3·s^-1
1	0.00832	340	8.3081	22.1351	2411.916
2	0.00799	353	8.0842	21.0259	2853.709
3	0.00664	423	7.1462	16.7883	3734.732
4	0.00426	653	5.2879	9.9271	13277.710
5	0.00440	635	5.4180	10.3682	6783.020
6	0.00753	372	7.7604	19.4411	6380.770

图8 间歇流流动示意图

图9 液层/气泡区截面图

图10 不同流量下的气团流图

图11 不同流量下的段塞流图

图12 液层/气泡区持液量与液相高度拟合结果

表3 模型误差分析

流量/L·min^-1	诱导时间实验值/s	诱导时间计算值/s	相对误差/%	平均相对误差/%
1.68	1803	1856.6	2.89	4.99
3.36	1647	1679.6	1.94
8.4	1530	1571.6	2.65
13.44	903	963.2	6.25
16.8	1167	1260.7	7.43
26.88	1407	1293.2	8.80

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