多相混输体系析蜡热力学研究进展

doi:10.11885/j.issn.1674-5086.2013.04.23.03

摘要/Abstract

摘要：

针对海底多相混输体系析蜡问题，开展了蜡热力学预测模型及析蜡实验测量方法的研究。通过对Won 模型、
Ji 模型等析蜡热力学预测模型的分析，认为热力学预测模型的建立过程中需考虑到液相描述一致性、固–固转变、纯组
分热力学性质、Poynting 修正项处理以及活度系数计算等问题。并对可用于多相体系析蜡实验测量的激光法、超声波
法、声共振法、石英晶体微天平法以及高压微差示扫描量热法等进行了分析研究。认为石英晶体微天平法因其较高的
灵敏性，高压微差示扫描量热法因其简便、耗样量少、再现性好且测试过程中基本避免了人为因素的影响，具有较好的
应用前景。

关键词: 多相, 蜡, 热力学模型, 实验方法, 混输体系

Abstract:

Wax precipitation in multiphase system was studied with wax thermodynamic models and experiment methods in
view of sea floor transportation system. Based the analysis of the wax thermodynamic models of Won and Ji’s，the consistency
of calculation method selecting of liquid phase fugacity in vapor-liquid equilibrium and liquid-solid equilibrium，solid-solid
transition，the thermodynamic properties of pure components，Poynting correction term treatment，as well as activity coefficient
calculation should be considered when a new model is built. Experimental measurement methods，such as laser method，
ultrasonic method，acoustic resonance method，quartz crystal microbalance method（QCM），high-pressure micro-differential
scanning calorimetry method（HP–µDSC），which can be used to the analysis of the multiphase system. The results show
that quartz crystal microbalance method has good prospect because of its high sensitivity，and high-pressure micro-scanning
calorimetry method because of its easy conduction，small sample consumption，good reproducibility and almost no influence
of human factors in the testing process.

Key words: multiphase, wax, thermodynamic model, experimental method, mixed transportation system

杨文，曹学文. 多相混输体系析蜡热力学研究进展[J]. 西南石油大学学报(自然科学版), DOI: 10.11885/j.issn.1674-5086.2013.04.23.03.

Yang Wen, Cao Xuewen. Thermodynamics Study Progress of Wax Precipitation in
Multiphase System[J]. 西南石油大学学报(自然科学版), DOI: 10.11885/j.issn.1674-5086.2013.04.23.03.

0
/ / 推荐

导出引用管理器 EndNote|Ris|BibTeX

链接本文: http://journal15.magtechjournal.com/Jwk_xnzk/CN/10.11885/j.issn.1674-5086.2013.04.23.03

http://journal15.magtechjournal.com/Jwk_xnzk/CN/Y2014/V36/I2/152

参考文献

[1] 中华人民共和国国土资源部资源概况：矿产资

源[EB/OL]//2012，http：//www.mlr.gov.cn/zygk/#.

[2] Won K W. Continuous thermodynamics for solid-liquid

equilibria：wax formation from heavy hydrocarbon mixtures[

C]. Houston：AIChE Meeting，1985.

[3] Won K W. Thermodynamics for solid solution-liquidvapor

equilibria：wax phase formation from heavy hydrocarbon

mixtures[J]. Fluid Phase Equilibria，1986，30：

265–279.

[4] Pedersen K S，Skovborg P，Roenningsen H P. Wax precipitation

from North Sea crude oils. 4. Thermodynamic

modeling[J]. Energy & Fuels，1991，5（6）：924–932.

[5] Pedersen K S. Prediction of cloud point temperatures and

amount of wax precipitation[J]. SPE Production and Facilities，

1995，10（1）：46–49.

[6] Hansen J H，Fredenslund A，Pedersen K S，et al. A thermodynamic

model for predicting wax formation in crude

oils[J]. AIChE Journal，1988，34（12）：1937–1942.

[7] Flory P J. Principles of polymer chemistry[M]. Cornell University

Press，1953.

[8] Lira-Galeana C，Firoozabadi A，Prausnitz J M. Thermodynamics

of wax precipitation in petroleum mixtures[J].

AIChE Journal，1996，42（1）：239–248.

[9] Nichita D V，Goual L，Firoozabadi A. Wax precipitation

in gas condensate mixtures[J]. SPE Production and Facilities，

2001，16（4）：250–259.

[10] Dalirsefat R，Feyzi F. A thermodynamic model for

wax deposition phenomena[J]. Fuel，2007，86（10）：

1402–1408.

[11] Broadhurst M G. An analysis of the solid phase behavior of

the normal paraffins[J]. J. Res. Natl. Bur. Stand. A，1962，

66：241–249.

[12] Coutinho J A P，Andersen S I，Stenby E H. Evaluation

of activity coefficient models in prediction of alkane

solid-liquid equilibria[J]. Fluid Phase Equilibria，1995，

103（1）：23–39.

[13] 陈五花，赵宗昌. 降凝剂对含蜡油石蜡析出过程影响

的实验与模型化研究[D]. 大连：大连理工大学，2009.

[14] Ji Hongyan. Thermodynamic modelling of wax and integrate

wax-hydrate[D]. Edinburgh：Heriot-Watt University，

2004.

[15] Coutinho J A P，Stenby E H. Predictive local composition

models for solid/liquid equilibrium in n-alkane systems：

Wilson equation for multicomponent systems[J]. Industrial

& Engineering Chemistry Research，1996，35（3）：

918–925.

[16] Coutinho J A P. Predictive local composition models：

NRTL and UNIQUAC and their application to model

solid-liquid equilibrium of n-alkanes[J]. Fluid Phase Equilibria，

1999，158：447–457.

[17] Morawski P，Coutinho J A P，Domańska U. High pressure

（solid+ liquid）equilibria of n-alkane mixtures：experimental

results，correlation and prediction[J]. Fluid Phase

Equilibria，2005，230（1）：72–80.

[18] Nasrifar K，Fani Kheshty M. Effect of pressure on the

solid-liquid equilibria of synthetic paraffin mixtures using

predictive methods[J]. Fluid Phase Equilibria，2011，

310（1）：111–119.

[19] Roenningsen H P，Bjoerndal B，Baltzer Hansen A，et

al. Wax precipitation from North Sea crude oils：1. crystallization

and dissolution temperatures，and Newtonian

and non-Newtonian flow properties[J]. Energy & Fuels，

1991，5（6）：895–908.

[20] Kok M V，Létoffé J M，Claudy P，et al. Comparison of

wax appearance temperatures of crude oils by differential

scanning calorimetry，thermomicroscopy and viscometry[

J]. Fuel，1996，75（7）：787–790.

[21] Calange S，Ruffier-Meray V，Behar E. Onset crystallization

temperature and deposit amount for waxy

crudes：experimental determination and thermodynamic

modelling[C]. SPE 37239，1997.

[22] Ruffier-Meray V，Roussel J C，Defontaines A D. Use

of pulsed nmr spectroscopy to measure the amount of

solid deposits as a function of temperature in waxy

crudes[J]. Oil & Gas Science and Technology，1998，53（4）：531–535.

[23] Schüller R B，Tande M，Almøy T，et al. A new statistical

method for determination of wax appearance temperature[

J]. Annual Transactions of the Nordic Rheology Society，

2009，17（1）：191–197.

[24] Henson F V，Roehner R. Measurement of wax precipitation

temperature and precipitated solid weight percent

versus temperature by infrared spectroscopy：U.S.6，841，

779[P]. 2005–1–11.

[25] Hammami A，Raines M A. Paraffin deposition from crude

oils：comparison of laboratory results with field data[J].

SPE Journal，1999，4（1）：9–18.

[26] 梅海燕. 油气体系有机固相沉积机理与热力学模型研

究[D]. 合肥：中国科学技术大学，2000.

[27] Meray V R，Volle J L，Schranz C J P，et al. Influence of

light ends on the onset crystallization temperature of waxy

crudes within the frame of multiphase transport[C]. SPE

26549，1993.

[28] De Boer R B，Leerlooyer K，Eigner M R P，et al. Screening

of crude oils for asphalt precipitation：theory practice

and the selection of inhibitors[J]. SPE Production & Facilities，

1995，10（01）：55–61.

[29] 张伟，郭平，谯英，等. 超声波测定固相沉积点研究[J].

西南石油学院学报，2006，28（1）：49–51.

Zhang Wei，Guo Ping，Qiao Ying，et al. Study of the solid

precipitation deter-mined by ultrasonic[J]. Journal of

Southwest Petroleum Institute，2006，28（1）：49–51.

[30] Colgate S O，Sivaraman A，Dejsupa C. Sonic speed and

critical point measurements in ethane by the acoustic

resonance method[J]. Fluid Phase Equilibria，1992，76：

175–185.

[31] Colgate S O，Sivaraman A，Dejsupa C. Acoustic cavity

method for sonic speed measurements in liquids and stock

tank oils[J]. Fluid Phase Equilibria，1992，79：221–229.

[32] Yarranton H W，Chen T，Thomas F B. Detection

of phase transitions with acoustic resonance technology[

C]//Canadian International Petroleum Conference.

Petroleum Society of Canada，2000.

[33] Sivaraman A，Imer D，Thomas F B，et al. Defining SLE

and VLE conditions of hydrocarbon fluids containing wax

and asphaltenes using acoustic resonance technology[C].

New Orlean：Spring National Meeting，1998.

[34] TieIian Chen. Detection of Phase Transitions with Acoustic

Resonance[D]. Canada：University of Calgary，2000.

[35] Sauerbrey G Z. Use of quartz vibration for weighing

thin films on a microbalance[J]. J. Physik，1959，155：

206–212.

[36] Burgass R，Tohidi B. Development and validation of

small volume multi-tasking flow assurance tool[C]. SPE

145946，2011.

[37] Cassiède M，Pauly J，Milhet M，et al. A quartz crystal

microbalance technique to study wax crystallization in the

presence of gas[J]. Measurement Science and Technology，

2008，19（6）：065704.

[38] Juyal P，Cao T，Yen A，et al. Study of live oil wax precipitation

with high-pressure micro-differential scanning

calorimetry[J]. Energy & Fuels，2011，25（2）：568–572.

[39] Le Parlou¨er P，Dalmazzone C，Herzhaft B，et al. Characterisation

of gas hydrates formation using a new high

pressure Micro-DSC[J]. Journal of Thermal Analysis and

Calorimetry，2004，78（1）：165–172.

[40] Gupta A，Lachance J，Sloan Jr E D，et al. Measurements

of methane hydrate heat of dissociation using high pressure

differential scanning calorimetry[J]. Chemical Engineering

Science，2008，63（24）：5848–5853.

[41] Lafond P G，Olcott K A，Dendy Sloan E，et al. Measurements

of methane hydrate equilibrium in systems inhibited

with NaCl and methanol[J]. The Journal of Chemical

Thermodynamics，2012，48：1–6.