Dynamic interfacial tensions in acidic crude oil/caustic systems. Part I: A chemical diffusion-kinetic model

AIChE Journal ◽  
1986 ◽  
Vol 32 (3) ◽  
pp. 455-466 ◽  
Author(s):  
R. P. Borwankar ◽  
D. T. Wasan
SPE Journal ◽  
2008 ◽  
Vol 13 (01) ◽  
pp. 5-16 ◽  
Author(s):  
Shunhua Liu ◽  
Danhua Zhang ◽  
Wei Yan ◽  
Maura Puerto ◽  
George J. Hirasaki ◽  
...  

Summary A laboratory study of the alkaline-surfactant-polymer (ASP) process was conducted. It was found from phase-behavior studies that for a given synthetic surfactant and crude oil containing naphthenic acids, optimal salinity depends only on the ratio of the moles of soap formed from the acids to the moles of synthetic surfactant present. Adsorption of anionic surfactants on carbonate surfaces is reduced substantially by sodium carbonate, but not by sodium hydroxide. The magnitude of the reduction with sodium carbonate decreases with increasing salinity. Particular attention was given to a surfactant blend of a propoxylated sulfate having a slightly branched C16-17 hydrocarbon chain and an internal olefin sulfonate. In contrast to alkyl/aryl sulfonates previously considered for EOR, alkaline solutions of this blend containing neither alcohol nor oil were single-phase micellar solutions at all salinities up to approximately optimal salinity with representative oils. Phase behavior with a west Texas crude oil at ambient temperature in the absence of alcohol was unusual in that colloidal material, perhaps another microemulsion having a higher soap content, was dispersed in the lower-phase microemulsion. Low interfacial tensions existed with the excess oil phase only when this material was present in sufficient amount in the spinning-drop device. Some birefringence was observed near and above optimal conditions. While this phase behavior is somewhat different from the conventional Winsor phase sequence, overall solubilization of oil and brine for this system was high, leading to low interfacial tensions over a wide salinity range and to excellent oil recovery in both dolomite and silica sandpacks. The sandpack experiments were performed with surfactant concentrations as low as 0.2 wt% and at a salinity well below optimal for the injected surfactant. It was necessary that sufficient polymer be present to provide adequate mobility control, and that salinity be below the value at which phase separation occurred in the polymer/surfactant solution. A 1D simulator was developed to model the process. By calculating transport of soap formed from the crude oil and injected surfactant separately, it showed that injection below optimal salinity was successful because a gradient in local soap-to-surfactant ratio developed during the process. This gradient increases robustness of the process in a manner similar to that of a salinity gradient in a conventional surfactant process. Predictions of the simulator were in excellent agreement with the sandpack results. Background Although both injection of surfactants and injection of alkaline solutions to convert naturally occurring naphthenic acids in crude oils to soaps have long been suggested as methods to increase oil recovery, key concepts such as the need to achieve ultralow interfacial tensions and the means for doing so using microemulsions were not clarified until a period of intensive research between approximately 1960 and 1985 (Reed and Healy 1977; Miller and Qutubuddin 1987; Lake 1989). Most of the work during that period was directed toward developing micellar-polymer processes to recover residual oil from sandstone formations using anionic surfactants. However, Nelson et al. (1984) recognized that in most cases the soaps formed by injecting alkali would not be at the "optimal" conditions needed to achieve low tensions. They proposed that a relatively small amount of a suitable surfactant be injected with the alkali so that the surfactant/soap mixture would be optimal at reservoir conditions. With polymer added for mobility control, the process would be an alkaline-surfactant-polymer (ASP) flood. The use of alkali also reduces adsorption of anionic surfactants on sandstones because the high pH reverses the charge of the positively charged clay sites where adsorption occurs. The initial portion of a Shell field test, which did not use polymer, demonstated that residual oil could be displaced by an alkaline-surfactant process (Falls et al. 1994). Several ASP field projects have been conducted with some success in recent years in the US (Vargo et al. 2000; Wyatt et al. 2002). Pilot ASP tests in China have recovered more than 20% OOIP in some cases, but the process has not yet been applied there on a large scale (Chang et al. 2006).


2015 ◽  
Vol 37 (8) ◽  
pp. 1178-1185 ◽  
Author(s):  
Zhao-Hui Zhou ◽  
Qun Zhang ◽  
Yan Liu ◽  
Hong-Zhuang Wang ◽  
Hong-Yan Cai ◽  
...  

2014 ◽  
Author(s):  
E. A. Cavanzo ◽  
S. F. Muñoz ◽  
A.. Ordoñez ◽  
H.. Bottia

Abstract In Situ Combustion is an enhanced oil recovery method which consists on injecting air to the reservoir, generating a series of oxidation reactions at different temperature ranges by chemical interaction between oil and oxygen, the high temperature oxidation reactions are highly exothermic; the oxygen reacts with a coke like material formed by thermal cracking, they are responsible of generating the heat necessary to sustain and propagate the combustion front, sweeping the heavy oil and upgrading it due to the high temperatures. Wet in situ combustion is variant of the process, in which water is injected simultaneously or alternated with air, taking advantage of its high heat capacity, so the steam can transport heat more efficiently forward the combustion front due to the latent heat of vaporization. A representative model of the in situ combustion process is constituted by a static model, a dynamic model and a kinetic model. The kinetic model represents the oxidative behavior and the compositional changes of the crude oil; it is integrated by the most representative reactions of the process and the corresponding kinetic parameters of each reaction. Frequently, the kinetic model for a dry combustion process has Low Temperature Oxidation reactions (LTO), thermal cracking reactions and the combustion reaction. For the case of wet combustion, additional aquathermolysis reactions take place. This article presents a full review of the kinetic models of the wet in situ combustion process taking into account aquathermolysis reactions. These are hydrogen addition reactions due to the chemical interaction between crude oil and steam. The mechanism begins with desulphurization reactions and subsequent decarboxylation reactions, which are responsible of carbon monoxide production, which reacts with steam producing carbon dioxide and hydrogen; this is the water and gas shift reaction. Finally, during hydrocracking and hydrodesulphurization reactions, hydrogen sulfide is generated and the crude oil is upgraded. An additional upgrading mechanism during the wet in situ combustion process can be explained by the aquathermolysis theory, also hydrogen sulphide and hydrogen production can be estimated by a suitable kinetic model that takes into account the most representative reactions involved during the combustion process.


1977 ◽  
Vol 17 (02) ◽  
pp. 122-128 ◽  
Author(s):  
W.H. Wade ◽  
J.C. Morgan ◽  
J.K. Jacobson ◽  
R.S. Schechter

Abstract The interfacial tension of surfactant mixtures with hydrocarbons obeys a simple scaling rule. Many apparently inert surfactants give low tensions when in mixtures; the scaling rule still applies to these mixtures. The influence of surfactant structure and molecular weight on low-tension behavior is examined, and the application of these results to the optimization of surfactant flooding systems is discussed. Introduction It has been shown that the interfacial-tension behavior of a given crude oil with a surfactant solution of the sulfonate type may be modeled by replacing the crude oil with one particular alkane. The number of carbon atoms in the alkane is referred to as the equivalent alkane carbon number (EACN) of the crude oil, and this EACN is independent of the surfactant used (at fixed standard conditions). This equivalency of a crude oil and an alkane is a result of the simple averaging behavior of hydrocarbons when mixed. Any hydrocarbon may be assigned an EACN value. For instance, when homologous series of alkyl benzenes and alkanes are run against the petroleum sulfonate TRS 10-80 at 2 gm/liter of surfactant with 10 gm/liter NaCl present, heptyl benzene and heptane, respectively, give minimum interfacial tensions, a. The EACN of heptyl benzene is 7, since it is equivalent to heptane. A simple averaging rule will give the EACN of a hydrocarbon mixture : (1) where x is the mole fraction of the ith component. Thus, an equimolar mixture of undecane (EACN 11) and heptyl benzene (EACN 7) has an EACN of 9. If a surfactant gives a low (minimum) sigma against nonane (EACN 9), it will also give a low sigma against the above mixture. Eq. 1 implies that a crude oil, which is a multicomponent hydrocarbon mixture, may be assigned an EACN. This has been verified experimentally. For example, Big Muddy field crude oil has an EACN of 8.5. Therefore, any surfactant phase giving a minimum tension against an equimolar mixture of octane and nonane gives a low tension against Big Muddy crude. All crude oils rested to date have EACN's ranging from 6 to 9. For a given surfactant, the alkane of minimum tension (min) may be affected by the electrolyte concentration or type, the temperature, the surfactant concentration, or the presence of a cosurfactant. These system variables may be adjusted until the nmin for a surfactant matches exactly the EACN of a crude oil. For any particular surfactant, many different combinations of variables will give the same n min value; therefore, there are many possible systems, each with n = EACN, available for crude oil recovery. In practice, however, the system variables may be manipulated to a limited extent only. The temperature of an oil field is fixed, and the surfactant concentration is limited by considerations of solubility and expense. The electrolyte concentration and type is partly determined by oilfield conditions and is limited by the effect on surfactant solubility. These limitations mean that many of the surfactants presently available on a large enough scale for use in low-tension flooding will not give minimum tensions in the range required (n of 6 to 9). This paper shows how minimal sigma's in the required range may be found for some of these "off-scale" surfactants when they are used in surfactant mixtures. The hypothesis tested here is that surfactant mixtures average in a manner analogous to the averaging of hydrocarbons in the oil phase. It will be shown that each surfactant component may be assigned an n value and that the alkane of minimum tension of a mixture of surfactants, (n), is then given by (2) where x is now the mole fraction of the ith component of the surfactant mixture. This greatly extends the number of surfactants that may be considered as candidates for use in low interfacial-tension flooding. SPEJ P. 122


2017 ◽  
Vol 159 ◽  
pp. 474-482 ◽  
Author(s):  
Qun Zhang ◽  
Shu-Yi Zhan ◽  
Zhao-Hui Zhou ◽  
Zheng-Xi Li ◽  
Wang-Hong Lu ◽  
...  

2017 ◽  
Vol 152 ◽  
pp. 602-610 ◽  
Author(s):  
Dan-Dan Zheng ◽  
Zhao-Hui Zhou ◽  
Qun Zhang ◽  
Lei Zhang ◽  
Yan Zhu ◽  
...  

1985 ◽  
Vol 29 (2) ◽  
pp. 409-415 ◽  
Author(s):  
A. Yermakova ◽  
E. M. Sulman ◽  
O. S. Popov ◽  
O. B. Sannikov ◽  
A. I. Gontar ◽  
...  

2005 ◽  
Vol 69 (18) ◽  
pp. 4505-4520 ◽  
Author(s):  
Yongchun Tang ◽  
Yongsong Huang ◽  
Geoffrey S. Ellis ◽  
Yi Wang ◽  
Paul G. Kralert ◽  
...  

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