The application claims, under 35 U.S.C. § 119(a), priority to and the benefit of Brazilian Patent Application No. BR 10 2022 022801 9, filed Nov. 9, 2022, which is incorporated by reference herein in its entirety.
The present invention relates to a method for predicting the restart of paraffinic oil flow by being able to estimate the paraffin precipitated fraction under conditions of production stoppage. This estimate is carried out through a simple equation with few parameters, which are obtained through differential scanning calorimetry (DSC) tests and rheological evaluation, to predict the yield stress (TLE) profiles in gelled paraffinic oil-containing pipes.
The method of the present invention is applicable in maritime oil production fields, more specifically in the flow assurance area of paraffinic oils and can be incorporated into flow assurance and computational fluid dynamics simulators to predict stress fields and production stoppage time.
Paraffinic crude oil contains significant amounts of paraffin compounds. These molecules are hydrocarbon mixtures known to produce a gel-like structure under specific circumstances when cooled below a critical temperature, known as the Initial Crystal Appearance Temperature (TIAC). The paraffin content may vary depending on the origin of the crude oil, however, there is evidence that with as little as 2.0% by mass of precipitated paraffin, gelling can occur (Hansen et al. [1]).
Furthermore, offshore oil production in deep waters involves numerous challenges, including the safe and efficient transportation of oil from the reservoir rock to the production platform. In this sense, paraffin precipitation and deposition cause detrimental effects on several aspects of crude oil processing. Paraffinic deposits formed on the pipe internal walls exposed to the low temperatures of the seabed increase in thickness and stiffness over time and limit the oil flow, increasing load losses necessary to produce it.
Furthermore, cooling, especially in quiescent conditions, such as during production stoppage, can lead to the appearance of a gelled structure. The formation of this structure in its turn causes drastic changes in the rheological properties of the fluid, such as the appearance of a yield stress (TLE) (Visintin et al. [2] and Paso et al. [3]). In these cases, restarting the production flow is only viable with the imposition of a pressure greater than the TLE. If the pressure available in the installation is lower than the TLE, the gel formed in the subsea line will block production, causing significant losses. In these cases, it is necessary to look for other ways to remedy the line blockage. Therefore, predicting the TLE value appropriately and the time to form the blockage is fundamental information for predicting operational conditions for restarting flow in paraffinic oil production fields.
Therefore, ensuring the flow of crude paraffinic oil is a major concern for the oil industry, especially on offshore platforms. On these platforms, paraffin precipitation and deposition is one of the widespread problems in oil industry operations around the world, with paraffin deposits creating problems from the wellhead to the refinery. Furthermore, these problems arise even when the oil is not in a completely gelled state. Thus, operations are hampered by the precipitation and deposition of paraffin in the well, in the pipes, in the drilling equipment, in the pump columns and rods, in addition to the transfer system and pipes (D. Tukenov [4]). The consequences are equipment failures, bottlenecks along the pipeline and loss of production, transportation and storage capacity, resulting in risky operations and lost revenue.
Currently, the prediction of production flow restart is often carried out by simulating the temperature profiles in the pipe during cooling. These profiles provide an estimate of the advancement of the crystallization frontier with time, as discussed in Bhat and Mehrotra [5], based on prior knowledge of the Initial Crystal Appearance Temperature (TIAC).
A second approach applied is the use of thermodynamic models to predict the precipitated fraction through direct correlations with temperature and pressure. Despite the validity of this approach, the thermodynamic models adopted are usually complex and depend on knowledge of information such as the distribution of the number of carbons of the paraffins present in the oil (Fleming et al. [6]). This distribution is obtained through gas chromatography experiments which can be noisy and difficult to read for crude oils.
Another relevant approach is that described in Mendes et al. [7], which presents a methodology for calculating yield stress (TLE) profiles in pipes containing gelled paraffinic oil. However, the stress profiles are obtained by direct correlations with the local temperature in the tube and the crystal appearance temperature (TIAC) of the oil, making it important in this scenario to apply kinetic models to predict the precipitated paraffin fraction.
Some kinetic models based on Avrami and Ozawa's theory are found in the literature (Zougari and Sopkow [8]). In this class of models, the kinetics are based on the crystallinity degree obtained from differential scanning calorimetry (DSC) experiments. But despite the validity of the model presented by Zougari and Sopkow [8], there is no mention of its application during stoppage problems.
In this sense, it is noted that differential scanning calorimetry (DSC) is an important technique applied to studies of oil paraffin precipitation in the context of flow assurance. This technique measures the heat flow to or from the sample when it is heated or cooled. Since crystallization releases heat, it will appear on the DSC curve as an exothermic peak during cooling. Thus, it is possible to quantify the thermal effects and measure thermodynamic data of paraffins. DSC is generally used to evaluate paraffin inhibition by heat flow, measurement of TIAC or to determine the mass fraction of crystals formed during cooling under quiescent conditions as a function of temperature.
The study by Zhao et al. [9] evaluates the thermal behavior of paraffinic oils using thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) techniques. Despite belonging to the same field as the proposed invention and making a correlation between the solid fraction of precipitated paraffin with the yield stress under production stoppage/restart conditions, Zhao et al. [9] does not take into account the paraffin fractions in the liquid phase. Furthermore, the yield stress calculation proposed by the Authors does not reconcile the precipitated paraffin fractions with the gel morphology and rheological properties.
Additionally, Zhao et al. [10] used DSC to investigate the effect of cooling rate, paraffin content, asphaltene and chemical additive on the TIAC of paraffinic oils and model crude oils. The results indicated that TIAC increases with increasing paraffin content. This confirms the greater precipitation in samples with higher paraffin content during the gelling process. However, the effect of pour point depressants on TIAC was greater than the other factors investigated.
Patent document FR 2976670 refers to a method for estimating the conditions for restarting the paraffinic oil flow in pipelines used to transport hydrocarbons and involves simulating the restart phase and evaluating the value of the hydrocarbon recirculation pressure in the pipeline. Although this is also associated with a methodology to calculate the ideal conditions for restarting production, the aforementioned document does not disclose or even suggest a kinetic model that reconciles the precipitated paraffin fractions and obtains the appropriate yield stress, taking into account the viscoelastic properties of paraffinic oils under cooling conditions inside the pipes.
Thus, the proposed method, object of the present invention, is an advance in the calculation of the yield stress in the tube due to the possibility of reconciling the precipitated paraffin fractions with the gel morphology through the fractal dimension property and with the rheological properties proposed by Shih et al. [11]. This new approach allows the results obtained to be interpreted as a function of time, by a kinetic model, through a consistent technical-scientific framework, thus providing reliability to the proposed method.
The present invention aims to reduce oil production losses resulting from the blockage of submarine lines as well as assist in reducing the costs of blockage remediation operations, which in extreme cases may require the replacement of part of the pipeline with gelled material. It is estimated that in these cases the cost of a single maintenance can reach around 30 million dollars (Huang et al. [12]).
Furthermore, the present invention aims to estimate the yield stress (TLE) to determine whether the pressure available in the installation for pumping the fluid in the line is capable of promoting the restart of flow. Finally, the information provided by the method is also useful for defining the premises of new production projects, being applicable to all maritime production fields.
The solution achieved by the proposed method is the possibility of predicting the precipitated paraffin fraction, under production stoppage conditions, through a simple equation with few parameters, which are obtained through differential scanning calorimetry tests and rheological evaluation, to predict yield stress profiles as a function of time in pipes containing gelled paraffinic oil. The time required for line blockage formation can also be obtained.
The present invention will be described below, with reference to the attached figures which, in a schematic way and not limiting the inventive scope, represent examples of implementation thereof.
The present invention relates to a method for predicting the restart of paraffinic oil flow capable of determining the yield stress (TLE) through the parameters of differential scanning calorimetry (DSC) tests and rheological evaluation of precipitated paraffin fraction under production stoppage conditions. Therefore, the invention is capable of estimating the yield stress (TLE) value appropriately and the time interval until the formation of the line blockage (i.e., the available waiting time), so as to guarantee the supply of accurate information on the operational conditions for restarting production of paraffinic oil production fields.
This estimate is made through equations 1 to 5, which reproduce the heat flow data (θ) corresponding to the phase transition of paraffins obtained by calorimetric analysis and obtaining the precipitated paraffin fraction (ϕPS).
Equation 1 represents the balance of precipitated paraffin fraction (ϕPS) as a function of temperature (T), which depends on a proportionality constant (k), the paraffin fraction in the oil (ϕ0) and an initial condition (ϕPS(Tinicial)=0).
Equation 2 represents the latent heat balance (θ) released by the sample during crystallization, which depends on the crystallization enthalpy of pure paraffin (Δhc=200 J/g), the cooling rate (q=−dT/dt) and an initial condition (θ (0)=0).
Equation 3 describes the linear temperature dynamics for cooling in DSC obeying the cooling rate imposed in the experiment (0.4 to 1.2° C./min), while Equations 4 and 5 describe the proportionality constant (k). This constant, in its turn, depends on a coefficient (kAR) and an activation function (kAT).
Regarding the values of the parameters used, the initial temperature (Tinitial) was determined as the Initial Crystal Appearance Temperature (TIAC) plus three (Tinitial=TIAC+3), obtained by calorimetry tests.
The other parameters, namely, kAR, AAT, EAT/R and ϕ0 were determined by the parameter estimation procedure adopted. In this procedure, based on data on time or temperature, heat flow and cooling rate, data on the fraction of precipitated paraffin are obtained indirectly, from Equation 1.
The estimation of the kinetic parameters, used in Equations 1 to 5, can be carried out using any commercial software or programming language, which allows the resolution of an algebraic-differential model and the application of an optimization method to minimize the square minimum function. Some examples include Matlab, FORTRAN, and Python languages.
To predict the yield stress (TLE) in pipes, a rheological assessment is carried out based on oscillatory stress amplitude scanning tests in rheometers for temperatures below the gelling temperature, as described in the works of Guimarães [13] and Marinho [14], in conjunction with differential scanning calorimetry tests. Then, a stress model based on the scaling theory of Shih et al. [11] is applied to adjust the precipitated paraffin fraction data, previously obtained in equations 1 to 5, with the rheological data, according to Equation 6. This model has two parameters to be adjusted, a proportionality factor (Cτ) and a structure factor, called fractal dimension (D):
Finally, the equations 2 can be incorporated into flow assurance and/or computational fluid dynamics simulators to predict stress profiles and available waiting time and define the conditions for restarting production in prolonged stoppage conditions. In general, the Marlim Transiente simulator, developed by Petrobras, can be used. However, other commercial flow simulators well known in the art can also be used.
Regarding the estimation of the parameters, in the present case, the non-commercial software called ESTIMA was used, in the FORTRAN programming language, developed in the Chemical Engineering Program at the Federal University of Rio de Janeiro. In this sense, it is noteworthy that time or temperature and heat flow data are provided to the estimator, and as a result of the optimization procedure, the model parameters are determined, whose suitability to the data can be evaluated by statistical parameters such as the determination coefficient R2.
Furthermore, the equation corresponding to the cooling of a pipe section is described in Equations 7 to 18.
Energy Balance:
in which, T is the temperature, t is the time, ρ is the mixture density, Cp is the heat capacity of the mixture, Rϕ is the source term corresponding to the kinetic model, r is the radial component, keff is the thermal conductivity of the mixture, U is the heat exchange global coefficient, T∞ is the seabed temperature and T0 is the initial temperature of the fluid.
In equations 11 to 14 there is the balance of paraffin in the liquid phase (ϕPL), in which Diff is the mass diffusivity of paraffin in the liquid phase and ϕPL,0 is the initial fraction of paraffin in the liquid phase.
In equations 15 to 18, there are the precipitated paraffin balance (ϕPS):
In general, based on differential scanning calorimetry data and rheological behavior, the kinetic behavior of the studied samples was evaluated by simulations of paraffinic oil production stoppages in a pipeline. The temperature profile, the paraffin fractions in the solid (crystallized) and liquid phases and the cooling rate were simulated in the period from zero to 14 days of quiescent cooling, for different heat exchange global coefficients (
Based on the profiles obtained in
The method proposed through equations 1 to 6 was applied in simulations of paraffinic oil production stoppages in the cross section of a pipeline, under the assumption of quiescent cooling. For this, an initial temperature of 60° C., a radius of 6 inches and an external seabed temperature of 4° C. were assumed, as shown in
The model for this simulation consists of the mass balance of crystallized paraffin fraction (ϕPS), the mass balance of liquid paraffin fraction ((PPL) and the energy balance in the section, represented by temperature (T).
Firstly, the kinetic model was adapted to the cooling problem in the section, according to Equations 7 to 10, in which Rϕ is the crystallization rate, t is the cooling time and r is the radial coordinate.
To describe the heat transfer in the tube section, a transient energy balance was adopted considering the radial dispersion of heat with the pipe, subject to a heat exchange global coefficient, according to Equations 11 to 14. In this balance, ρ represents the oil density, Cp the heat capacity, keff the thermal conductivity, t is the time, r is the radial coordinate, T∞ the temperature outside the tube, U the heat exchange global coefficient and r0 the radius of the tube:
For industrial application purposes, the U coefficient can be explained in terms of the characteristics of the tube, namely the thickness and conductivity of the wall and the insulating material and the external convection coefficient.
Finally, the mass balance for the liquid paraffin fraction, also with radial dispersion, was coupled to the model. As hypotheses, the absence of mass flow in the tube wall was adopted and that the proposed kinetic model acts as a source term, removing the crystallized paraffin fraction from the liquid phase. Equations 15 to 18 represent the model, in which ϕPL is the liquid paraffin fraction and Diff is the diffusivity of paraffin in the oil.
To solve these equations, the diffusive terms were discretized using the finite volume method and the resulting differential equations were integrated over time to obtain the temporal profiles. It is important to highlight that the proposed simulation can, without loss of validity, be carried out in commercial flow simulators, adding the kinetic model as a source term for the mass balance and applying rheological models to calculate the flow stress profiles as a post-processing step.
The parameters used in the simulations, obtained with the parameter estimation procedure from rheological and calorimetry data, are in Table 1.
The other parameters used represent typical values for the properties of paraffinic oils indicated in Mendes et al. [7] and Mehrotra et al. [15], according to Table 2.
As the first result of the proposed simulations, the radial profiles of temperature, paraffin fraction in the liquid phase, solid/crystallized paraffin fraction and cooling rate over 14 days of cooling for a crude sample supplied by Petrobras are presented in
From the radial profiles, the average profiles in the section are calculated over time, as shown in
Similarly, using rheological models as a post-processing step for the results, radial and average yield stress profiles are obtained from the radial profiles of crystallized paraffin fraction, as shown in
The stress profiles presented in
Therefore, the ability to predict the evolution of the precipitated paraffin fraction together with the viscoelastic properties of paraffinic oils under cooling conditions inside submarine pipes is of great use:
In this way, a reduction in oil production losses resulting from the occurrence of blockages by paraffinic oil in subsea lines during a production stoppage is expected and, also, a safer, more economical and efficient production.
Number | Date | Country | Kind |
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BR1020220228019 | Nov 2022 | BR | national |