Heavy Crude Oil Viscosity Reduction and The Impact of Asphaltene Precipitation

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Article
Heavy Crude Oil Viscosity Reduction and
the Impact of Asphaltene Precipitation
Osamah Ali Alomair, and Abdulwahab Salem Almusallam
Energy Fuels, Just Accepted Manuscript • Publication Date (Web): 04 Nov 2013
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Page 1 of 39 Energy & Fuels
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4 Heavy Crude Oil Viscosity Reduction and the Impact
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6 of Asphaltene Precipitation
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12 Osamah A. Alomair1* and Abdulwahab S. Almusallam2
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14 Department of Petroleum Engineering, 2Department of Chemical Engineering, College of
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Engineering and Petroleum, Kuwait University
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21 ABSTRACT
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One of the main challenges associated with the production of heavy or extra-heavy crude
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26 oil is transportation of the oil by pipelines, particularly without the prior reduction of the oil
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28 viscosity to acceptable values to ensure oil fluidity in the pipelines. The reduction of viscosity
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31 can be obtained by various sophisticated methods. In this study, we investigated different
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33 blending techniques to reduce the viscosity of heavy crude oil. The blending of Middle East
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35 heavy crude oil with light crude oil or with one of its distillates, such as kerosene or diesel, as
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38 diluents was conducted over the entire range of weight fractions at 20°C and atmospheric
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40 pressure. The heavy oil viscosity was decreased from 4,000 to 500 cP, representing an 88%
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reduction. The experimental data were fitted with an empirical equation, and the results were
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45 satisfactory, with an average absolute value of the deviation of 0.0015 cP. A negative
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47 performance of the heavy oil with diluent mixtures was identified based on the asphaltene
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50 precipitation phenomenon, which was found to depend on not only the type and composition of
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53 *Corresponding Author. Phone: +965-24987456; Fax: +965-24849558; P.O. Box Safat 13060,
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56 Kuwait. E-mail: dr.alomair@ku.edu.kw
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the diluents used but also the concentration of each diluent. To obtain additional insight into
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6 asphaltene precipitation, qualitative studies were performed with scanning electron microscopy
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8 imaging and dynamic light scattering. Compared to the other diluents, kerosene distillates
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performed well with a specific heavy crude oil sample under our testing conditions. The addition
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13 of 0.5-2 wt. % of a solvent mixture of polar protic hexane-1-ol and non-polar toluene to the
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15 crude oil and diluent mixture was found to successfully delay the precipitation of asphaltene in
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18 these low-viscosity mixtures.
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Keywords: Heavy Crude Oil, Light Crude Oil, Viscosity, Dilution, Asphaltene
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23 Precipitation, Pipeline, Crude Oil Transportation.
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29 1. INTRODUCTION
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32 One of the major difficulties in efficiently and economically transporting oil through a
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34 pipeline is the issues caused by the high viscosity of the ﬂuids.1 Heavy crude oil (HO) represents
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36 at least half of the recoverable oil resources of the world. HO is defined as complex ﬂuids of 10
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39 < API gravity < 20, with a viscosity at room temperature that varies from 102 cP to over 105 cP
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41 according to the International Energy Agency (IEA) and US Geological Survey (USGS).1,2
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These characteristics can cause a variety of difficulties during the production, separation, and
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46 transportation of HO. Efficient and economical methods are needed to reduce the viscosity of
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48 HO to enable the transportation of crude oil through pipelines. Crude oil with a viscosity close to
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51 500 cP is the classical maximum desired pipeline viscosity.2-5
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54 The most commonly used methods for reducing the viscosity of crude oil include heating,
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56 emulsification, and dilution with light crude oil (LO) or various fractions of LO. Heating is a
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typical method for overcoming the problems associated with HO transportation via a pipeline.6
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6 Thermal method like steam injection, or miscible solvent methods, (solvent into a pre-heated
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8 reservoir), are used for heavy crude oil and bitumen in oil field production. Steam generation
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costs and water production affect the economics of the thermal technique critically. Miscible
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13 methods are energy effective but their economics depends on the solvent recovery.7,8 Also
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15 heating crude oil to a significant temperature reduces its viscosity and makes it easier to pump
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18 and transport through pipelines. However, this method faces some problems, such as the high
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20 capital and operational costs of heated pipelines over long distances9 and the practical difficulty
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22 of maintaining both pumping and heating stations.10,11 Another method utilized in the
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25 transportation of HO is the formation of emulsions.12-14 In this method, the HO is suspended in a
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27 continuous water phase by the use of surfactants and detergents, forming an oil/water emulsion
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and thus achieving a reduction in the apparent viscosity (the ratio of shear stress to the rate of
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32 shear for a non-Newtonian fluid).15,16 The main difficulty of this technology is the selection and
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34 cost of the surfactant component of the emulsion, in addition to the cost of separation once the
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37 destination point of the pipeline is reached.10, 17
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39 Dilution is one of the oldest and most widely preferred methods for reducing the viscosity
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41 of HO. Until the end of the 1980s, natural gas condensates were used as diluents for the
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44 transportation of nearly the entire production of Canadian crude.18-20 The complexity of these
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46 processes, the availability of the condensate, and the condensate production are related to the
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48 demand for natural gas.18,21 Further, these products are poor solvents for asphaltenes, and
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51 flocculation may occur, which can lead to the partial plugging of lines and tanks.20, 22
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53 Consequently, when brought to ambient conditions, a deposit of black, highly viscous, and
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corrosive organic material solidifies quickly as a dry powder in facilities and pipelines.23 As a
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result, a high fraction of the cost associated with treatment operations is necessary and must
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6 include a corrosion inhibitor and control of the natural gas dew point and water content.
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8 Another choice is the dilution of HO with LO or its distillates, such as naphtha (Nt),
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kerosene (Kr), or diesel (De), to reduce the oil viscosity and facilitate its mobility in pipelines. A
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13 solvent fraction of 20–30% is often sufficient to avoid high pressure drops or the need for high
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15 temperatures,24 but a negative effect may occur in the form of asphaltene flocculation,
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18 aggregation, and sedimentation. It is assumed that asphaltene is suspended as a nano-colloid in
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20 crude oil25-26 and that this colloid consists of particles that are approximately 3 nm in diameter.
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22 Under a typical condition, such as changes in temperature, pressure, or composition, an increase
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25 in the aggregate size of asphaltene may occur, eventually leading to the precipitation of large
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27 asphaltene aggregates.27
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When the heavy oils were blended with the most aromatic diluents, precipitation and
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32 fouling were negligible. As the aromaticity of the diluents was decreased, the extent of
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34 asphaltene precipitation and the fouling rates increased. Also smaller molecules or molecules
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37 with the correct physical and chemical characteristics able to fit into the gaps between the
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39 asphaltene agglomerates can reduce the viscosity to a greater extent27. This is caused by deeper
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41 penetration, which induces greater breakup of the asphaltene agglomerates.
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44 Based on a literature survey, few authors 24-27 have considered specific crude oil samples.
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47 The physicochemical properties of crude oil vary from one oil field to another; in addition, the
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49 asphaltenes in a single sample of oil are poly-disperse, exhibiting a variety of physical properties,
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including molecular weight and aromaticity. Thus, it is important to study and understand the
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54 dilution performance of the HO that is specific to the region under consideration, which impacts
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56 the ability to enhance its specific flow properties. Further, understanding and controlling the
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process of asphaltene precipitation has proven to be a challenging task due to the diverse nature
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6 of asphaltenes and the variety of conditions under which the asphaltene phase can be separated
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8 from solution. By using the high depth of focus of a scanning electron microscope (SEM) to
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interpret the variation in the SEM image intensity, the SEM imaging technique can obtain
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13 qualitative information on the surface topography of the asphaltenes extracted from HO and LO.
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15 Consequently, the objective of this study is to reduce the viscosity of HO to the classical
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18 maximum desired pipeline viscosity and to understand the behavior of HO mixed with diluents
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20 without using any commercial inhibitors, which are typically expensive and of unknown
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22 composition. All of the HOs and associated diluent samples used in this study were collected
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25 from the same local area of production and refining. The viscosity of the tested HO and each
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27 diluent was measured, and the accuracy of the data was evaluated. The agreement between the
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observed and predicted viscosity values was assessed using an empirical model that relates the
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32 kinematic viscosity to the absolute temperature by a logarithmic function.28, 29 The viscosity data
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34 were determined for the experimental mixtures of the HO with different diluents, i.e., HO with
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37 LO, Kr, or De, over the entire range of weight fractions at 20°C and atmospheric pressure. Some
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39 problems arose during the measurements when attempting to decide which mixing rule is a better
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41 fit for the experimental viscosity data of each system. Among the rules reported in the literature
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44 are pure rules (Riazi et al.,30 Centeno et al.,31 Miadonge et al.32) and those with additional
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46 parameter mixing (Twu and Bulls,33 Lederer,34 Shu,35 ). A model that was proposed by Lederer34,
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based on a modified version of the classic Arrhenius expression was used with a high degree
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51 of accuracy. To understand the diluent performance in each system and to determine how to
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53 retard or reduce its impact on asphaltene precipitation, various concentrations of a polar protic
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solvent, hexane-1-ol, with a non-polar solvent toluene were used in the solvent mixture.
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Furthermore, the crude oil mixture behavior in each system was studied using dynamic light
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6 scattering, and the diluent effect on the change of hydrodynamic diameter of the flocculate due to
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8 asphaltene aggregation was monitored. Finally, the current study investigated the ability of the
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solvent mixture to move the system under study to a region of the phase in which asphaltene
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13 sedimentation will not occur.
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16 2. EXPERIMENTAL SECTION
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19 2.1. Materials. Samples of dry heavy Kuwaiti crude oil (HO), Kr, De, and light Kuwaiti
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crude ol (LO) were collected in specially designed glass stoppered bottles of 2.5-L capacity and
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24 were stored at 20°C. Kr and De were filtered using a 0.45-µm Polyfluortetraethylene (PTFE)
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filter to remove any suspended material. The HO and LO were mixed with an emulsion breaker
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29 (commercial-grade Nalco demulsifier), centrifuged to remove the traces of basic sediments and
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31 water (BS&W), and finally maintained in an oven at 25°C. As soon as the bottles were opened,
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the water contents of the samples were measured with a Metrohm KF (model 832-Thermoprep),
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36 and the moisture range was measured to be between 18·10-4 to 3·10-3 g·g-1. Several important
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38 physical and chemical properties (density, kinematic and dynamic viscosities, molecular weight,
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41 and elemental components) were measured, and the results are provided in Table 1.
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2.2. Viscosity and Density Measurements. Each sample mixture was prepared based on
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46 the mass by mixing the calculated volumes of HO with the calculated weight of each diluent, i.e.,
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48 LO, De, and Kr, in air-tight, stoppered glass bottles. An electronic balance with precision of ±
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51 10-4 g was used for the mass measurement. A set of a four concentrations of 5, 10, 15, and 20
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53 wt.% of each diluent (LO, Kr, and De) were mixed with HO. The dynamic viscosity (η),
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55 kinematic viscosity (υ), and density (ρ) measurements of both aforementioned hydrocarbons and
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58 their mixtures were determined immediately after sample preparation using a digital Anton Paar
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viscometer. The instrument calibration was performed by a triplicate measurement of the two
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6 synthetic standard oil samples (supplied by a manufacturer), which represent the high and low
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8 ranges of the viscometer, respectively, at the temperature range of interest with a reproducibility
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of ± 0.35% in the measuring range. The estimated uncertainty in the dynamic viscosity
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13 measurements was determined to be 3.8·10-3 mPa·s or less, with a confidence interval value of
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15 95% for all measurements. In addition, the instrument was calibrated for density using dry air
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18 and ultra-pure water, and the calibration was performed with an error rate within the range of ±
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20 0.5 Kg⋅m-3. Temperature control of the instrument was achieved using a solid-state thermostat
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and two integrated Pt-100 temperature sensors with a temperature reproducibility of ± 10-2°C.
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25 Under the same conditions of 1 atm. and 20°C, the density of the asphaltenes can be estimated
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27 from the following equation, as proposed by Luo & Gu37:
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30 w asp
31 ρasp = , (1)
32 1 1 − w asp
−
33 ρoil ρ mal
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36 where ρoil are the measured densities of original HO and LO samples and wasp weight percent of
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38 asphaltene of these crude oil samples (see Table1). The measured densities of maltenes
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41 extracted from the HO and LO are ρmal = 954.27 and 818.14 kg⋅m-3, respectively.
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43 2.3. Chromatographic Analysis. The boiling points distribution and carbon numbers of all
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45 samples were examined with an Simulated Distillation (SIMDIS) Analyzer using the ASTM
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48 D2887 method for low-temperature tests and the D6352, D7500, and D7169 methods for high-
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50 temperature tests. The SIMDIS analyzer uses a non-polar chromatographic column that separates
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the hydrocarbons in order of their boiling points. These hydrocarbons are correlated with the
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55 retention times through a calibration curve obtained by running a known mixture of
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57 hydrocarbons, typically n-alkanes, under the same conditions and covering the boiling range
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expected in the sample. The analysis yielded the final boiling point values (253, 444, 716, 603,
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6 and 719°C) and the total carbon numbers from C35 to C100 (0.0, 0.0, 50.8, 28.4, and 71.8 mol %)
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8 for Kr, De, HO, LO, and asphaltene, respectively. These analyses indicating that Kr and De
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diluent do not contain asphaltene fractions, whereas the HO and LO samples do contain
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13 asphaltene (see Figure 1 and the elemental analysis section of Table 2).
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16 2.4. Elemental Compositions and Molecular Weight Measurements of All Pure Samples.
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19 Elemental analysis (CHNS) of HO, LO, Kr, De, and asphaltene was performed using a MICRO
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21 cube (GmbH). The instrument was first calibrated with a suitable standard, such as
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23 sulfamethazine and acetanilide, as recommended by the ASTM D5291 method. The final
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26 products were detected by a thermal conductivity detector (TCD) for C, H, and N and by an
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28 infrared detector (IR) for S. The molar ratio of hydrogen to carbon (H/C) can be determined from
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the elemental analysis and molecular weight, and the ratio is used to determine the degree of
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33 carbonization, as provided in Table 1. The molar H/C ratios of the asphaltenes extracted from
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35 LO and HO were 2.07 and 1.93 respectively.
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39 The asphaltene samples extracted from LO and HO contain less N and more S than the
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41 original LO and HO samples. The molecular weights for all samples examined were measured
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43 using an instrument based on the freezing point depression technique. The precision of the
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46 temperature measuring system was attained by calibration with a standard of pure hydrocarbons
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48 with known freezing points and molecular weights. The observed depression of the freezing
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point temperature was used to calculate the molecular weight of the solute (oil) samples.
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54 2.5. Particle Sizing by Dynamic Light Scattering (DLS). The DLS technique measures
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56 fluctuations in the intensity of the scattered light due to the motion of molecules in solution. A
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photomultiplier tube is used to measure the instantaneous intensity, and computer software is
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6 used to convert the intensity fluctuations into an autocorrelation function. The resulting
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8 correlation function may be inverted to determine the size distribution of the particles in solution.
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The diameter that is measured in DLS is called the hydrodynamic diameter, and it refers to how a
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13 particle diffuses within a fluid. The diameter obtained by this technique is that of a sphere that
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15 has the same translational diffusion coefficient as the diffusion coefficient of the particles. The
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18 apparatus used in this work was equipped with a He-Ne laser (632.8 nm, Max 4mW.) that uses a
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20 backscattering angle of 173°. The equipment was set up to automatically detect the particle size
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22 every 5 min, with the measurement repeated up to 200 times. The HO was mixed with micro-
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25 pore-filtered Kr, De, LO, or mixed solvent in specific proportions and then placed in a glass
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27 cuvette. The measurement was initiated immediately after sample equilibration in the light
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scattering chamber at 20°C.
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33 2.6 Asphaltene Content and Surface Topography. Asphaltenes are commonly
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35 accepted as being components of crude oil with a boiling range from 400-700°C; they are
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38 insoluble in n-heptane and dispersed in toluene or benzene.38 However, other definitions are
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40 based on the use of a different precipitating solvent, such as n-hexane and/or n-pentane.39 An
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42 important aspect of asphaltene preparation is the proportion of crude-oil/n-heptane used for
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45 precipitation. Some investigators40,41 follow a modification of ASTM procedure D2007 that
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47 involves precipitation of the asphaltenes using a ratio of 1:10, whereas other researchers42 use a
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proportion of 1:40. Consequently, the experiments presented here were performed using a
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52 modification of the methods of (Yarranton et al. and the ASTM method).43,45 The crude oil
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54 samples (10 g) were shaken overnight with a GFL orbital shaker (Model 3005, UK) to ensure
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homogeneity. Normal heptane was then added at the ratio of 40 ml to 1 g of the sample in an
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appropriate flask, followed by shaking for 10 min. Then, the mixture was left to rest overnight.
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6 Asphaltene was removed from solution by vacuum filtration through a Whatman 934-AH glass
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8 microfiber filter, measuring 15 cm in diameter, with a pore size of 1.5 µm. All of the asphaltenes,
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including the material adhering to the filters and filter surfaces, were dissolved with excess
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13 toluene. The filtrate was concentrated to a minimal volume using a rotary evaporator. The
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15 filtered asphaltenes were dried in a vacuum oven at 60°C for 24 h and maintained in the fume
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18 hood for 2 days. The weight of the asphaltenes was determined as follows:
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Weight of dried asphaltene ( g )
22 Asphaltene content = x 100
23 Crude oil weight ( g ) . (2)
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28 The surface topography of the extracted asphaltene samples was studied using a field-
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30 emission scanning electron microscope (FE-SEM) operating at a low vacuum pressure of 9.6·10-5.
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32 The asphaltenes were dried in a vacuum oven at a temperature of 105°C for 20 min and then
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35 sputter-coated with gold before the SEM examination. Digital SEM images of the asphaltene
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37 particles obtained from the HO and LO samples were taken at magnifications of 100×, 500×,
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1,000×, and 1,500× (see Figures 2a and b). Irregularly shaped accumulated particles were
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42 observed in the HO asphaltene samples, with a size range of 1 µm to 20 nm, whereas a particle
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44 range of 1 µm to 10 nm was observed for the LO asphaltene samples. Higher-magnification
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imaging exhibited randomly distributed pores. To determine the main elements in LO and HO
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49 asphaltene samples. The localized chemical analysis was done by surfaces X-ray spectrum using
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51 energy dispersive spectroscopy (EDS). The results revealed that (C) and (S) are the major
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54 constituents of the asphaltenes. Also traces of sodium (Na) and chlorine (Cl) were found. In
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56 addition to small amount of vanadium (V) and oxygen (O), as listed in Table 4…
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6 3. RESULTS AND DISCUSSION
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9 From an economic perspective, any improvement in the dilution efficiency will be
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12 beneficial to the handling of crude oil because this approach will reduce the amount of solvent
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14 necessary to obtain an acceptable viscosity that enables the transport of large quantities of heavy
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16 oil. For this reason, the authors of this work are searching for efficient solvents.
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19 3.1. Evaluation of the Blank and Mixed Hydrocarbon Experimental Viscosity Data
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23 a. Blank HO, LO, Kr, and De samples. An empirical model applicable to most oils under normal
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25 working conditions28,29 has been used to predict viscosities of tested samples. It relates the
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27 kinematic viscosity to the absolute temperature by a logarithmic function:
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30 log log (υT + 0.7 + cT )  = A + B log T , (3)
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34 where cT is a parameter that varies with the value of υT and has the value of zero when υT ≥ 1.5
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36 mm2·s-1, and A and B are composition-dependent constants (see Table 5). This viscosity-
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39 temperature expression may be presented in a linear form. To determine the degree of linear
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41 correlation of the variables (the goodness of fit) and how the independent variable predicts the
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43 dependent variable, the R2 was calculated via a regression analysis. The appropriateness of the
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46 model increased as R2 approaches the value of one:
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49 R 2 = SS M (SS M + SS E ) , (4)
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52 where SSM is the sum of the squares of the distances between the regression points and the data
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55 average and SSE is the sum of the squares of the distances between the experimental points and
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regression points. The calculated R2 values indicate that the regression data correlations are well
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6 suited to the experimental data (see Table 5).
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9 b. Mixtures of HO and diluents. The estimation of the viscosity of mixtures is today one of the
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11 most difficult problems. Now, the problem arises when trying to decide which one of the mixing
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14 rules is better to use among those reported in the literature. So to the best of our knowledge and
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16 from the practical view point a modified version of the classic Arrhenius expression, proposed
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18 by Leaderer34 was more satisfactory to represent our experimental viscosity of the mixtures;
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21
22  αV ο   αV ο 
log µ =   log µο + 1 −  log µs
 αV ο + V s   αV ο + V s 
23 (6)
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25
26
27
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29 where the parameter α is an empirical constant whose value ranges from zero to one. Fitting the
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31 experimental data with a least-squares method leads to α values of 0.5821, 0.6031, and 0.5211
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34 for HO with LO, Kr, and De systems, respectively, with low standard deviation values (σ) of
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36 0.065, 0.031, and 0.022, respectively. These values were calculated using the following equation:
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39
 1/2
40  n 
2
41 
 ∑ ( Y exp − Y cal) 

 
42 σ= i =1  , (7)
43 


(n − p ) 


44  
45  
 
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Figure 3 presents the results of the dynamic viscosity of HO diluted with LO, De, and Kr as
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51 functions of diluent concentration. The lines in the figure indicate the predictions generated using
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53 the Lederer equation34. Shu et al.35 proposed an expression for α to represent the viscosity of HOs
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4
or bitumen diluted with light hydrocarbons. They correlated this parameter with (ρo, µO) and (ρs,
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6 µS) of the oil (o) and diluents (s), respectively, as follows:
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9
17.04 ( ρο − ρs )
0.5237
10 ρο3.2745 ρs1.6316
11 α= , (8)
12 µ 
ln  ο 
13
 µs 
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18 The calculated values of α using Equation 8 are 0.5797, 0.599, and 0.5239 for HO with
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21 LO, Kr, and De, respectively. These values agreed with those obtained by fitting the experimental
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23 data of the viscosity of the mixtures with the % relative differences of 0.431, 0.68, and 0.536,
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25 respectively, calculated as follows:
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27
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29 x1 −x 2
30 % Difference =
31
 x1 +x 2 
  (9)
32  2 
33
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35 The agreement between the experimentally obtained values of α and the theoretical values
36
37 indicate that the obtained viscosity data were highly accurate.34
38
39
40 3.2. HO Viscosity Reduction. As presented in Figure 3, the concentration of diluents
41
42
43 increases and the mixture viscosity decreases up to the conventional maximum desired pipeline
44
45 viscosity values at the optimum concentrations of 15 wt.% for Kr and 20 wt.% for either LO or De
46
47 diluents in HO. Thus, the diluents can be ranked in terms of their relative ability to reduce the
48
49
50 viscosity of HO as Kr > De and LO.
51
52
53 3.3. The Behavior of HO Mixtures
54
55
56 a. HO + Kr diluent. Several studies have characterized crude oil and the structure of
57
58
59
60
13
1
2
3
asphaltene.40-43 Unfortunately, variations in the percentage of paraffinic and aromatic
4
5
6 hydrocarbons, poly-aromatic complex rings, and short side chains in each diluted crude oil system
7
8 affect asphaltene precipitation. The average particle sizing (APD) method was used to understand
9
10
11
the result of HO/diluent ratios on the colloidal properties of asphaltenes and their aggregation
12
13 phenomena.
14
15
16 Figure 4 presents the behavior of the HO samples with different percentages of Kr used
17
18 as the diluent. The blank HO sample has an APD range from 1-3 nm. After a certain period of
19
20
21 time, the asphaltene gradually started to flocculate, aggregate, and form sediment at 5 wt.% Kr at
22
23 an APD value of 40 nm. As the diluent concentration in HO was increased to 10 wt.%, the APD
24
25 initially increased to 80 nm. Further, as the diluent concentration was increased to 15 wt.% in
26
27
28 HO, the APD exhibited an initial increase to 90 nm, followed by precipitation and sedimentation
29
30 with APD values of 20 and 10 nm, respectively.
31
32
33 Understanding and controlling the phenomenon of asphaltene precipitation has proven to
34
35
36 be a challenging task due to the diverse nature of the asphaltenes and the variety of conditions
37
38 under which asphaltenes separate from solution. Not only do asphaltenes vary from one oil field
39
40 to another, but the asphaltenes within a single sample of oil also poly-disperse and exhibit a
41
42
43 range in terms of their physical properties, such as their molecular weight and aromaticity.26
44
45 Several researchers have assumed that asphaltene particles remain dispersed in crude oils due to
46
47 the interactions between the natural surfactant polar groups (resins) and superficial charges on
48
49
50 the asphaltene.26, 27, 40 Others have proposed a hypothetical asphaltene structure that contains
51
52 double or even triple plates, which are thought to contain a fused ring system and are attached by
53
54
55
alkyl chains.41-44 Thus, when the concentration of the diluents increases in the aforementioned
56
57 system by over 5%, the balance among the aromatic and paraffinic hydrocarbons are thought to
58
59
60
14
1
2
3
be disturbed; as a result, the resin desorbs from the asphaltene layers, causing the asphaltene
4
5
6 flocculates to grow in size. Eventually, large asphaltene aggregates precipitate out of the
7
8 solution.
9
10
11 To delay or avoid this behavior, many commercial aggregation inhibitors are available on
12
13
14 the market with high prices and unknown chemical compositions; similarly, their compatibility
15
16 with the systems under consideration is also unknown. Thus, in this work, one of our goals was
17
18 to use known and available good polar solvents. Argillier et al.36 investigated the role of the polar
19
20
21 component of hexane-1-ol on asphaltene properties. The results of their work indicated that the
22
23 minimum values for the radius of asphaltene gyration could be observed when using a hexanol in
24
25 toluene mixture with 10 vol.% as a solvent. Consequently, our study focused on testing synthetic
26
27
28 solutions prepared from 8, 11, and 13 vol.% of extracted HO asphaltene particles completely
29
30 dissolved in toluene. The particles size distribution of asphaltene in toluene solution in each
31
32
33
prepared synthetic sample was measured using DLS. Positive results involving a decrease in the
34
35 asphaltene particle size from 1,000 nm to approximately 200 nm were observed, as shown in
36
37 Figure 5. The decrease in the asphaltene particle size that could be seen in these results may be
38
39
40 due to the ability of hexanol to establish hydrogen bonds via polar interaction with the
41
42 asphaltenes, thereby inhibiting some of the asphaltene-asphaltene interactions.
43
44
45
46
47 According to Hildebrand,46 who laid the foundation for solubility theory based on the
48
49 inter-solubility of two materials with similar intermolecular attractive forces, one might also
50
51
expect components with similar cohesive energy density values to be miscible. As a result, it is
52
53
54 necessary to calculate the solubility parameter for HO and the mixed solvent to better understand
55
56
57
58
59
60
15
1
2
3
the behavior of asphaltene. The Hildebrand solubility parameter of the solvent mixtures does, δo
4
5
6 = (dispersion part δd, + polar part δp + hydrogen bonding part δh) can be calculated as follows:
7
8
9 n
10 δo = ∑ δ i V i (10)
11 i =1
12
13
14
15 A simplified correlation presented by Lange47 was used to estimate the HO solubility parameter
16
17 δo in (cal⋅cm-3)0.5 = 0.4888 ⋅ ( δο ) in (MPa)1 2 from the average molecular weight of the oil (MW)
18
19
20 and its temperature T (°C) as follows:
21
22
23
24 δ o = 0.01⋅ ( MW ) + 6.54 − 0.01⋅ (T − 25) (11)
25
26
27
28
Equation 10 was used to calculate the solubility parameter of the mixed solvent at the
29
30 proposed percentage of 13 vol.% of hexane-1-ol in toluene, and Equation 11 was used to calculate
31
32 the solubility parameter for HO; the values obtained for the solubility parameter of the mixed
33
34
35 solvent and HO were 21.552 and 21.75 MPa1/2, respectively. Consequently, the mixed solvent is a
36
37 suitable solvent for HO. As a result, different concentrations of the solvent mixture were added to
38
39 the system under study until the optimum value was attained.
40
41
42 Figure 6 presents the effect of the solvent mixture added on the aggregation/sedimentation
43
44 performance of HO mixed with Kr at 15%. At mixed solvent concentrations of 0.5 and 0.75 wt.%,
45
46
identical behaviors of asphaltene aggregation were observed, with an APD value of 90 nm for the
47
48
49 flocculates, followed by precipitation and finally sedimentation, with an APD range of 20-40 nm.
50
51 At 1.2 wt.% mixed solvent value, the APD of the aggregates was of the same value, i.e., 90 nm,
52
53
54
but decreased to an APD value of 60 nm, which did not exhibit any subsequent precipitation or
55
56 sedimentation during the testing period (400-1,000 min).
57
58
59
60
16
1
2
3
4
5
6 This decrease suggests that the solution stability can be attained when all possible polar
7
8 sites of asphaltene, which contains O, N, and S, are able to associate with the alcohol functional
9
10
11
group (OH); the remainder of the mixed solvent acts as an inhibitor with respect to increased
12
13 flocculate radius due to increasing interactions between the solvent and asphaltene and the
14
15 breaking of the asphaltene-asphaltene interactions, which are responsible for the large particle
16
17
18 diameters. Consequently, the small decrease in the particle diameter, observed from 90 to 60 nm,
19
20 can be attributed to a decrease in the aggregate density when a mixed solvent of the appropriate
21
22 quantity was added.
23
24
25 b. HO + De diluent. Figure 7 presents the behavior of the HO and De mixture with a
26
27
28 diluent concentration of 5-20%. The asphaltenes started to flocculate and aggregate within periods
29
30 of 150, 130, and 100 min with APD values of 20, 30, and 50 nm, respectively. This performance
31
32 was followed by precipitation and sedimentation, with an APD value close to 20 nm. As soon as
33
34
35 the fraction of De diluent reached 20%, the asphaltenes started to flocculate, aggregate, and
36
37 precipitate rapidly, i.e., within 10 min, with an APD value of 30 nm; subsequently, the asphaltenes
38
39
began to form sediment, with an APD value of 10 nm after 100 min. The maximum APD value
40
41
42 for HO with De was less than that for HO with Kr, with a difference of 50 nm. According to the
43
44 GC analysis of the pure diluents, Kr has a 7.5% higher aromatic content and 9% lower paraffin
45
46
47
content (normal, iso-, and cyclo-) than those of De (see Table 3).
48
49
It is possible that the decrease in the time responses of precipitation and sedimentation and
50
51
52 the decreased APD of the De system are due to the influence of hydrocarbon composition and/or
53
54 the density difference between the asphaltene aggregates and the bulk of the mixture. To delay or
55
56
57
eliminate asphaltene precipitation, a mixed solvent (13 vol.% hexane-1-ol in toluene) was added
58
59
60
17
1
2
3
stepwise to the HO with the De diluent system, up to a value of approximately 1.7 wt.%.
4
5
6 Consequently, asphaltene flocculates remained suspended with an average diameter of 60 nm over
7
8 a period of 400-1,000 min. The same result can be observed as that obtained in the HO system
9
10
11
with 15 wt.% Kr when 1.2 wt.% of the synthetic mixed solvent was added, as observed in Figure
12
13 6. This result suggests that not only did the mixed solvent affect the asphaltene behavior; the
14
15 diluent composition also altered the precipitation and sedimentation processes.
16
17
18 c. HO + LO. Figure 8 depicts the performance of HO diluted with the calculated limit
19
20
21
value of 20% LO, from the beginning with asphaltene until the aggregation, precipitation, and
22
23 sedimentation of particles occurred, with an APD of 25 nm, within 30 min. To delay the
24
25 asphaltene precipitation and sedimentation of the HO+LO system, a synthetic mixed solvent with
26
27
28 values of 1.7 and 2 wt.%, respectively, was used. Consequently, the asphaltene flocculants started
29
30 to increase in size and were subsequently suspended in solution, with an average particle diameter
31
32 of 60-65 nm, as found in the Kr and De systems with the mixed solvent. According to the GC
33
34
35 analysis, the asphaltene, HO, and LO phases contain different molar proportions of high-
36
37 molecular-weight fractions of (C35 to C100) with average mass fractions of 0.718, 0.508, and 0.284
38
39
respectively, (see Table 2). In addition, the molar H/C ratios of asphaltene extracted from LO and
40
41
42 HO were 2.069 and 1.928 respectively, along with the presence of a few wt.% of N, S, and O.
43
44 The results indicate that asphaltene hydrocarbon compositions based on hydrogen bonding with
45
46
47 polar functional groups may be responsible for increasing the attractive π-π inter-plate interaction
48
49 and the flocculent particle size. This suggests that, as the asphaltene particles approach each other
50
51
in a parallel arrangement, higher density difference were occurs between the aggregated particles
52
53
54 and the bulk solution. Consequently these will lead to the precipitation and sedimentation of the
55
56 aggregated particles. The degree to which the aggregate sizes vary is controlled by the
57
58
59
60
18
1
2
3
polydispersity and chemistry of the asphaltene monomers.
4
5
6 Although the chemical analyses performed in this work provide valuable information
7
8
9 concerning the chemistry of asphaltene and offer possible mechanisms of interaction, the
10
11 techniques do not directly probe the colloidal properties of the asphaltenes. As a result, it is
12
13
believed that the asphaltene activities of each system depend on not only the interactions between
14
15
16 the aggregates but also changes in the composition of the crude oil mixtures. Consequently, it
17
18 would be helpful to investigate the behavior of HO with asphaltene-free LO diluent crude oil
19
20
21
samples. To perform this test, asphaltene was extracted and completely separated from the
22
23 samples using a modification of ASTM procedure D2007. The remaining samples are a mixture of
24
25 saturated, aromatic, and resin hydrocarbons (maltene). Figure 7 presents the behavior of the two
26
27
28 systems of HO blended with 20% maltene of LO as the diluent. In addition, LO was blended with
29
30 20% maltene of HO. No asphaltene precipitation was detected in either of these two systems. The
31
32 structures remained stable for each mixture throughout the entire period of 1,000 minutes, with
33
34
35 average particle diameters of 3-5 nm. Therefore, the use of LO maltene is the best method for the
36
37 stabilization of HO. It is important to consider the expensive nature of the industrial separation
38
39
process of asphaltene from crude oil relative to the cost of using only synthetic solvent with
40
41
42 diluents.
43
44
45 4. CONCLUSION
46
47
48
49 By studying the various alternatives for reducing the viscosity of HO to enhance its flow
50
51 properties and meet the pipeline viscosity specifications, blending HO with a limited amount of
52
53 diluents at 20°C was found to be the most appropriate and favorable method. The accuracy of the
54
55
56 experimental viscosity data measurements of the blank, diluents, and mixtures of diluents with
57
58
59
60
19
1
2
3
HO were studied, with the results being satisfactory, yielding low absolute values for the
4
5
6 deviations. The addition of optimum diluent weight percentages in the range of 15-20 wt.% of Kr,
7
8 De, or LO to HO led to a viscosity reduction of 82-88% relative to its original value. However,
9
10
11
this option remains a challenge because it requires the use of the diluents at concentrations higher
12
13 than the threshold concentration for controlling the pressure drop in pipelines. Changing the
14
15 oil/diluent ratio may affect the composition and properties of the oil, which can lead to the
16
17
18 phenomenon of asphaltene flocculation, eventual sedimentation, and pipeline clogging.
19
20
21 The ranking of the amount of flocculation was observed to be HO with De > HO with LO
22
23 > HO with Kr, with aggregates of the average particle size depending on not only the composition
24
25
26 but also the diluent concentration. No effect of the maltene hydrocarbon on the intrinsic colloidal
27
28 structure of HO was observed in the current study.
29
30
31
32
A synthetic mixed solvent of a ratio in the range of 10-13 vol.% hexanol in toluene is more
33
34 valuable than using unknown commercial inhibitors for reducing the viscosity of HO in the oil
35
36 field when mixed with any hydrocarbon diluent by the optimum percentage of 1.2-2 wt.%. This
37
38
39 solvent was able to reduce the flocculent nanostructures and to delay or stop asphaltene
40
41 sedimentation.
42
43
44 All the results are valid for specific crude oil and its distillates of the same physicochemical
45
46
47 properties. It cannot be extrapolated but it can be used as a good guide to replicate the study for
48
49 any crude oil to be transported. Because the difference in nature of hydrocarbons in the crude,
50
51
the polydispersivities and polarities of resin. Also the asphaltene in a single sample of oil are
52
53
54 lipophilic with respect to aromatics, in which they form highly scattered colloidal solutions with
55
56 variety of physical properties. So it is highly recommended to perform lab compatibility tests
57
58
59
60
20
1
2
3
before blending a HO with a diluent, in addition to studying the asphaltene behavior of crude oil
4
5
6 mixtures for specific oil fields.
7
8
9
10
11
12
13 ACKNOWLEDGEMENTS
14
15 The authors are grateful for the help and support received from the Kuwait University
16
17 General Facility Research, Grants GE 01/07 and GE 03/08.
18
19
20 NOMENCLATURE
21
22 A, B = intercept and slope of eq 3
23
24
R2 = coefficient of determination
25
26
27 T = absolute temperature in Kelvin, (K)
28
29 Vo and Vs = volume fraction of oil (o) and diluents (s)
30
31
32
Vi = molar volume of pure solvent, (cm3·mol-1)
33
34 Yexp, Ycal = experimental and calculated dynamic viscosity
35
36 υT = kinematic viscosity, (mm2⋅s-1)
37
38
39 µo, µs = dynamic viscosities of oil (o) and diluents (s), (mPa·s)
40
41 α = empirical constant
42
43
44 σ = standard deviation
45
46 n, p = number of data points and coefficients
47
48
49
ρo, ρs = density of oil (o) and diluents (s), (kg·m-3)
50
51 δo and δi = Hansen parameters46 of the mixture and pure solvent, (MPa)1/2
52
53
54
55
56
57
58
59
60
21
1
2
3
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44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
25
1
2
3
4
5
6 Table 1. The Physical Properties of the Crude Oil Samples, Diluents, and Extracted Asphaltene
7
8 Property Heavy Light Kerosene Diesel Asphaltene Asphaltene
9 Crude Oil Crude Oil (LO) (HO)
10
11 Density @ 20°C / (Kg·m-3) 982 833 765 825 1153 1465
12
13
Dynamic Viscosity @ 20°C / 3900 4.0 1.3 5.6 - -
14
15
16 (mPa·s)
17
18 Kinematic Viscosity @ 20°C 3972 4.8 1.7 6.8 - -
19
20 / (mm2·s-1)
21
22
23 Elemental Analysis,
24
25
26
(mass fraction)
27
28 Carbon (C) 0.867 0.860 0.856 0.841 0.811 0.810
29
30 Hydrogen (H) 0.082 0.099 0.139 0.131 0.140 0.130
31
32
33 Sulfur (S) 0.046 0.037 0.003 0.026 0.048 0.058
34
35 Nitrogen (N) 0.005 0.004 0.002 0.002 0.001 0.002
36
37
Molar (H/C) 1.13 1.38 1.95 1.87 2.07 1.93
38
39
40 Molecular weight (g·mol-1) 411 220 159 229 4031 4117
41
42 Asphaltene wt.% 8.0 5.0 - - - -
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
26
1
2
3
Table 2. The Compositional Analysis Results of Kr, De, HO, LO, and Asphaltene
4
5
6 Carbon Number Kerosene Diesel Heavy Light Asphaltene
7
8 Crude Oil Crude Oil
9
10
11 Average mass fractions
12
13
C6-C16 0.950 0.350 0.113 0.353 0.009
14
15
16 C16-C27 0.050 0.605 0.250 0.259 0.050
17
18 C28-C30 0.000 0.022 0.053 0.050 0.125
19
20 C31-C34 0.000 0.023 0.075 0.054 0.098
21
22
C35-C78 0.000 0.000 0.369 0.215 0.235
23
24
25 C79-C98 0.000 0.000 0.119 0.059 0.270
26
27 C99-C100 0.000 0.000 0.021 0.010 0.213
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
27
1
2
3
Table 3. The Hydrocarbon Types Present in Kr and De Diluents
4
5
6
7 Kerosene Diesel
8 Hydrocarbon Type
9
10 mole fractions mole fractions
11
n-Paraffin 0.313 0.441
12
13 iso-Paraffin 0.230 0.175
14
15 Naphthenic 0.245 0.082
16
17 Aromatic 0.211 0.080
18
19 Unknowns 0.001 0.067
20
21 Saturates C15+ 0.000 0.155
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
28
1
2
3
4
Table 4. The Elemental Composition Values Derived from Six Spectrum Analyses of HO and LO
5
6 Asphaltene Samples Using EDS*
7
8 Designation Elemental
9 C O Na S Cl V Total
10 composition,
11
12
13 values
14
15 Mass fractions
16
Maximum
17
18
19 values 0.884 0.035 0.004 0.088 0.007 0.006 -
20
21 Average of
22 HO
23
24 six spectrum 0.875 0.029 0.004 0.084 0.006 0.002 1.000
25
26 Minimum
27 0.867 0.019 0.003 0.08 0.006 0.001
28 values
29 -
30
31 Maximum
32
33 values 0.875 0.035 0.005 0.116 0.008 0.004 -
34
35
36 Average of
37 LO
38 six spectrum 0.855 0.028 0.004 0.105 0.006 0.002 1.000
39
40 Minimum
41 0.845 0.012 0.002 0.092 0.005 0.001
42
43 values -
44
45
46 *Localized chemical analysis by surfaces X-ray spectrum
47
48
49
50
51
52
53
54
55
56
57
58
59
60
29
1
2
3
4
5
6
7
8
9
10
11 Table 5. The Linear Coefficients A and B and Mean Absolute Percentage Error
12 (MAPE) and R2 of Equation 3 for the Blank Component
13
14
15 Designation A B MAPE R2
16
17
18 HO
19
-9.494 -3.622003 0.7484 0.920
20
21
22 LO -0.233 -0.000052 0.3375 0.934
23
24
25
26
Kr -0.505 -0.000678 0.0999 0.975
27
28
29 De -0.155 -0.00026 0.0595 0.981
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
30
1
2
3 Table 6. Physical Properties of HO, LO, Kr, and De in the Temperature Range of 20-60 °C.
4
5
6 Temp. Dynamic Kinematic Density Dynamic Kinematic Density
7
Viscosity Viscosity Viscosity Viscosity
8
9 mPa·S mm2·S-1 mPa·S mm2·S-1
10
11
12
13 °C (cP) (cSt) Kg·m-3 (cP) (cSt) Kg·m-3
14
Heavy Crude Oil Light Crude Oil
15
16 20 3900 3972 982 4.00 4.8 833
17
18
19
25 2448 2500 979 3.56 4.3 828
20
21 30 1503 1542 975 3.13 3.8 823
22
23 40 673 695 969 2.52 3.1 813
24
25
26 50 330 343 963 2.09 2.6 804
27
28 60 177 185 956 1.75 2.2 796
29
30 Kerosene Blank Diesel Blank
31
32 20 1.30 1.7 765 5.60 6.8 825
33
34
25 1.22 1.6 761 4.85 5.9 823
35
36
37 30 1.14 1.5 758 4.18 5.1 819
38
39 40 0.98 1.3 752 3.25 4.0 812
40
41
42
50 0.97 1.3 745 2.66 3.3 805
43
44 60 0.81 1.1 739 2.15 2.7 798
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
31
1
2
3
4 800
5 kerosene
6 Diesel
7 700
8
Heavy Oil
9 Light Oil
600
10 Asphaltene in CS2
11
Temperature C
12 500
o
13
14
15 400
16
17 300
18
19
20 200
21
22
23
100
24
25 0
26
27 0 20 40 60 80 100
28 Volume Distillat %
29
30
31 Figure 1 The boiling ranges of Kr, De, HO, LO, and Asphaltene in CS2.
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
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60
32
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50 (a) HO-Asphaltene (b) LO-Asphaltene
51
52 Figure 2 (a) The microscopic structures of the HO asphaltenes (908 kPa) as observed using the
53
54 SEM at 100×, 500×, and 1,000× magnifications. (b) The microscopic structures of the LO
55
56
57 asphaltenes in the SEM at 100×, 1,000×, and 1,500× magnifications.
58
59
60
33
1
2
3
4
5
6
7
8
9 4500
10
11 Heavy Oil + Kerosene
12
4000
Heavy Oil + Diesel
13 Heavy Oil + Light Oil
Dynamic Viscosity of Crude Oil + Diluent
14 3500
15
16
17 3000
18
19 2500
20
(mPa.s)
21
22 2000
23
24 1500
25
26
27 1000
28
29 500
30
31
32 0
33 0 2 4 6 8 10 12 14 16 18 20 22
34
35 Weight % of Diluent
36
37
38 Figure 3 The effect of diluent concentration on the dynamic viscosity of the liquid mixtures,
39
40
41 where the solid line represents data predicted using the Leaderer viscosity model.
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
34
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
Figure 4 The effect of mixing 5, 10, and 15 wt.% kerosene with HO on asphaltene flocculation
34
35 and grain size distribution over time.
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
35
1
2
3
4
5
6
1100
7 Asphalten + toluene 8 vol.% hexanol
8 1000
9 11 vol.% hexanol 13 vol. % hexanol
10
Z-Average Partical Diameter, nm
900
11
12 800
13
14 700
15
16 600
17
18 500
19
20 400
21
22 300
23
200
24
25 100
26
27 0
28
29 0 100 200 300 400 500 600 700 800 900 1000 1100
30 Time min
31
32
33 Figure 5 Effect of the hexanol-to-toluene ratio on the asphaltenes practical size distributions in
34
35
36 the synthetic solution.
37
38
39
40
41
42
43
44
45
46
47
48
49
50
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60
36
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30 Figure 6 The effect of adding synthetic mixed solvent (hexanol-to-toluene ratio of 13:100) for
31
32 the mixture of HO +15 wt.% kerosene diluent on asphaltene flocculation and grain size
33
34
distribution over time.
35
36
37
38
39
40
41
42
43
44
45
46
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49
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37
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30 Figure 7 The effect of diluent concentration De and adding 1.7 wt.% synthetic mixed solvent on
31
32
33 HO asphaltene flocculation and grain size distribution over time.
34
35
36
37
38
39
40
41
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1
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13
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15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33 Figure 8 The effect of mixed solvent and maltene amounts on asphaltene flocculation and grain
34
35 size distribution over time.
36
37
38
39
40
41
42
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44
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39

Heavy Crude Oil Viscosity Reduction and The Impact of Asphaltene Precipitation

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