FIELD

[0001] The invention relates to a process for upgrading heavy oil and/or bitumen.

Specifically, the process relates to a process for de-asphalting heavy oil and/or bitumen.

BACKGROUND

[0002] Heavy oil and/or bitumen are often difficult to transport from production sites due to high viscosities at typical handling temperatures. They generally need to be diluted by the addition of at least one low density and low viscosity diluent to make the heavy oil and/or bitumen transportable, particularly when transporting over long distances.

[0003] There are several disadvantages of adding diluent to heavy oil and/or bitumen to produce transportable oil including: availability of diluents, typically light hydrocarbons, such as gas condensates, is steadily decreasing worldwide, making them more expensive to procure; and the diluent takes up pipeline space without adding value.

[0004] For example, in Canada, when making transportable oil and using gas condensate as a diluent, the volume of gas condensate added to the bitumen is typically 30 to 35% of the total product.

[0005] One method for addressing the difficulties for handling heavy oil and/or bitumen is solvent de-asphalting. Solvent de-asphalting is a process that removes the asphaltenes fraction from a hydrocarbon feed using a solvent. Solvent de-asphalting is described in, and amongst other sources, the article by Billon and others published in 1994 in Volume 49, No. 5 of the journal of the French Petroleum Institute, pages 495 to 507, in the book "Raffinage et conversion des produits lourds du petrole [Refining and Conversion of Heavy Petroleum

Products]" by J. F. Le Page, S. G. Chatila, and M. Davidson, Edition Technip, pages 17-32. Exemplary solvent extraction processes, for effecting the de-asphalting, are described in U.S. Patent No. 7,597,794.

[0006] When the solvent is mixed with the hydrocarbon feed in an extractor,

asphaltenes (which are insoluble in certain solvents) precipitate from the mixture. These precipitated asphaltenes are recovered from the bottom of the extractor, while the remaining hydrocarbons are recovered along with the solvent from the top of the extractor. The solvent is then separated from the remaining hydrocarbons. This asphaltene-lean hydrocarbon stream has improved properties compared to the original hydrocarbon feed due to the reduction or elimination of undesirable asphaltenes.

[0007] JS Buckley et al, "Asphaltene Precipitation and Solvent Properties of Crude Oils",

(1998) 16:3-4 Petrol Sci and Tech 251 show that the prediction of the onset of asphaltene precipitation at ambient conditions may be improved using refractive index (Rl) to characterize crude oils and their mixtures with precipitants and solvents. However, Buckley does not teach the significance of Rl at solvent de-asphalting process conditions, which occur after the onset of precipitation and at higher temperatures and pressures.

[0008] K Akbarzadeh et al, "A generalized regular solution model for asphaltene precipitation from n-alkane diluted heavy oils and bitumens", (2005) 232 Fluid Phase Equilibria 159 discloses a solvent de-asphalting model. However, these models are not very robust, rely on parameters that cannot be easily measured or estimated, and have low accuracy.

[0009] There exists a need for improved solvent de-asphalting systems and methods.

SUMMARY

[0010] In one aspect, there is provided a method for solvent de-asphalting including selecting a solvent based on Rl and contacting the selected solvent with a feed including asphaltenes to effect de-asphalting.

[0011] In another aspect, there is provided a de-asphalting system for solvent de- asphalting including a deasphalter and a controller. The deasphalter defines a contacting zone for contacting a feed, including asphaltenes, and a solvent to form a mixture, where the contacting of the feed and the solvent causes at least a portion of the asphaltenes to precipitate out of the mixture, the contacting disposed at an operating temperature; and a separation zone to separate the mixture into a de-asphalted oil-comprising material fraction ("S+PDAO") and a asphaltene-rich material fraction, the asphaltene-rich material fraction including the precipitated asphaltenes. The controller controls at least one operating parameter of the deasphalter based on at least on a refractive index of the S+PDAO phase. The operating parameter is selected from: the operating temperature; the composition of the feed; the composition of the solvent; a ratio of the mass of precipitated asphaltenes to the mass of asphaltenes within the feed; and a ratio of the mass of the solvent to the mass of the feed. [0012] In some embodiments, the de-asphalting system further includes at least one flow regulator operatively connected to the controller for controlling a feed flow rate of the feed, a solvent flow rate of the solvent or both.

[0013] In some embodiments, the de-asphalting system further includes a temperature regulator operatively connected to the controller for controlling the operating temperature of the contacting zone.

[0014] In some embodiments, the de-asphalting system further includes a refractive index determining device operatively connected to the controller for determining the refractive index of the S+PDAO.

[0015] In some embodiments, the refractive index determining device is a refractometer.

In some embodiments, the refractive index determining device is a densitometer.

[0016] In some embodiments, the refractive index of the S+PDAO is calculated as a function of the portion of the precipitated asphaltenes, the refractive index of the feed composition, the refractive index of the solvent, the UOP-K characterization factor of the solvent, and the operating temperature according to the following formulas:

[0017] In another aspect, there is provided a method for solvent de-asphalting including providing a feed, including asphaltenes, at a feed flow rate; providing a solvent at a solvent flow rate; contacting the solvent and the feed at an operating temperature to effect precipitation of at least a portion of the asphaltenes to obtain a S+PDAO and an asphaltene-rich material fraction, where the asphaltene-rich material fraction, includes the precipitated asphaltenes; and controlling one operating parameter based on at least a refractive index of the S+PDAO, the operating parameter selected from: the operating temperature, the composition of the feed, the composition of the solvent, a ratio of the precipitated asphaltenes to the mass of asphaltenes within the feed, and a ratio of the feed flow rate to the solvent flow rate.

[0018] In another aspect, there is provided a deasphalted oil obtained by a method including the steps of: providing a feed, including asphaltenes, at a feed flow rate; providing a solvent at a solvent flow rate; contacting the solvent and the feed at an operating temperature to effect precipitation of at least a portion of the asphaltenes to obtain a S+PDAO and an asphaltene-rich material fraction, wherein the asphaltene-rich material fraction includes the precipitated asphaltenes; and controlling one operating parameter based on at least a refractive index of the S+PDAO, the operating parameter selected from: the operating temperature, the composition of the feed, the composition of the solvent, a ratio of the precipitated asphaltenes to the mass of asphaltenes within the feed, and a ratio of the feed flow rate to the solvent flow rate.

[0019] In another aspect, there is provided a method for solvent de-asphalting including: defining at least the following operating parameters: a composition of a feed including asphaltenes, a target ratio of a mass of removed asphaltenes to the mass of asphaltenes within the feed, an operating temperature for contacting the feed and a solvent, and a ratio of a feed flow rate of the feed to a solvent flow rate of the solvent; determining an Rl of the solvent based at least on calculating the Rl of a S+PDAO formed by contacting the feed with the solvent;

selecting a solvent based at least on the determined solvent Rl; and contacting the selected solvent with the feed at the operating parameters to effect de-asphalting.

[0020] In another aspect, there is provided a method for starting up a solvent

deasphalting process including: pre-determining four operating parameters, the operating parameters are selected from: an operating temperature, a composition of a feed, a composition of a solvent, a target ratio of a mass of precipitated asphaltenes to a mass of asphaltenes initially within the feed, and a ratio of a feed flow rate to a solvent flow rate; determining the non- predetermined operating parameter based on at least an expected Rl of an S+PDAO stream generated by the process; and starting up the process using the pre-determined operating parameters and the determined operating parameter.

BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 shows a system for de-asphalting according to an embodiment.

[0022] Figure 2 shows a method for de-asphalting according to an embodiment. [0023] Figure 3 shows a product obtained by a method for de-asphalting according to an embodiment.

[0024] Figure 4 shows a method for de-asphalting according to an embodiment.

DETAILED DESCRIPTION

[0025] This disclosure is based in part on the surprising discovery that a solvent de- asphalting process can be characterized and/or controlled based at least on refractive index ("Rl") of a product stream.

[0026] In one aspect, there is provided a system for de-asphalting 100 (Figure 1 ). The de-asphalting system 100 includes a deasphalter 101. A feed 104, including asphaltenes 104a, and a solvent 106 are contacted within a contacting zone 103 of the deasphalter 101 to form an intermediate mixture 107. The contacting zone 103 is disposed at an operating temperature. The asphaltenes 104a are insoluble in the solvent 106, and at least a portion of the asphaltenes 110a will precipitate out of the mixture 107. The mixture 107, resulting from the contacting, is separated in a separation zone 109 of the deasphalter 101, into at least a deasphalted oil- comprising material fraction ("S+PDAO") 108 and an asphaltene-rich material fraction 110. In this context, the use "at least" suggests that there may be other fractions that are also separated. The asphaltene content of the deasphalted oil-comprising material fraction 108 is less than the asphaltene content of the feed 104. The asphaltene-rich material fraction 110 includes the precipitated asphaltenes 110a.

[0027] The de-asphalting system 100 includes a controller 112 for controlling at least one operating parameter of the de-asphalting system 100 based on at least a Rl of the S+PDAO 108. The operating parameter is selected from: the operating temperature; the composition of the feed 104; the composition of the solvent 106; a ratio of the mass of the precipitated asphaltenes 110a to the mass of the asphaltenes 104a within the feed; and a ratio of the mass of the solvent 106 to the mass of the feed 104.

[0028] In some embodiments, the feed 104 is a heavy hydrocarbon-comprising material.

The heavy-hydrocarbon-comprising material may be liquid, semi-solid, or solid, or any combination thereof. [0029] In some embodiments, for example, the heavy hydrocarbon-comprising material is a material that includes at least 10 weight percent of hydrocarbon-comprising material that boils above 500°C. In some of these embodiments, for example, the heavy hydrocarbon- comprising material is a material that includes at least 20 weight percent of hydrocarbon- comprising material that boils above 500°C. In some of these embodiments, for example, the heavy hydrocarbon-comprising material is a material that includes at least 30 weight percent of hydrocarbon-comprising material that boils above 500°C. In some of these embodiments, for example, the heavy hydrocarbon-comprising material is a material that includes at least 40 weight percent of hydrocarbon-comprising material that boils above 500°C. In some of these embodiments, for example, the heavy hydrocarbon-comprising material is a material that includes at least 50 weight percent of hydrocarbon-comprising material that boils above 500°C. In some of these embodiments, for example, the heavy hydrocarbon-comprising material is a material that includes at least 60 weight percent of hydrocarbon-comprising material that boils above 500°C. In some of these embodiments, for example, the heavy hydrocarbon-comprising material is a material that includes at least 70 weight percent of hydrocarbon-comprising material that boils above 500°C. In some of these embodiments, for example, the heavy hydrocarbon-comprising material is a material that includes at least 80 weight percent of hydrocarbon-comprising material that boils above 500°C. In some of these embodiments, for example, the heavy hydrocarbon-comprising material is a material that includes at least 90 weight percent of hydrocarbon-comprising material that boils above 500°C. In some of these embodiments, for example, the heavy hydrocarbon-comprising material is a material that boils above 500°C.

[0030] In some embodiments, for example, the heavy hydrocarbon-comprising material includes a Conradson carbon residue content of at least 12 weight percent, based on the total weight of the heavy hydrocarbon-comprising material. In some of these embodiments, for example, the heavy hydrocarbon-comprising material includes a Conradson carbon residue content of at least 13 weight percent, based on the total weight of the heavy hydrocarbon- comprising material. In some of these embodiments, for example, the heavy hydrocarbon- comprising material includes a Conradson carbon residue content of at least 14 weight percent, based on the total weight of the heavy hydrocarbon-comprising material. In some of these embodiments, for example, the heavy hydrocarbon-comprising material includes a Conradson carbon residue content of less than 30 weight percent, based on the total weight of the heavy hydrocarbon-comprising material. [0031] in some embodiments, for example, the heavy hydrocarbon-comprising material includes an asphaltene content of less than 40 weight %, based on the total weight of the heavy hydrocarbon-comprising mixture. In some of these embodiments, for example, the heavy hydrocarbon-comprising material includes an asphaltene content of less than 20 weight %, based on the total weight of the heavy hydrocarbon-comprising mixture. In some of these embodiments, for example, the heavy hydrocarbon-comprising material includes an asphaltene content of less than 15 weight %, based on the total weight of the heavy hydrocarbon- comprising mixture.

[0032] In some embodiments, for example, the asphaltenes are C5-asphaltenes.

C5-asphaltenes are material precipitating from a hydrocarbon composition after being mixed with 40 volumes of an n-pentane (n-C5) solvent at room temperature. The C5-asphaltene content of the heavy hydrocarbon-comprising material composition can be determined using ASTM D6560, modified to use pentane as the solvent.

[0033] In some embodiments, for example, the heavy hydrocarbon-comprising material includes an inorganic solids content of less than 1 weight %, based on the total weight of the heavy hydrocarbon-comprising mixture. In some of these embodiments, for example, the heavy hydrocarbon-comprising material includes an inorganic solids content of less than 0.5 weight %, based on the total weight of the heavy hydrocarbon-comprising mixture.

[0034] In some embodiments, for example, the inorganic solids of the heavy hydrocarbon-comprising material were micrometer (10 ^"6 m) size particles. In some embodiments, for example, the inorganic solids in the heavy hydrocarbon-comprising material were nanometer (10 ^~9 m) size particles.

[0035] In some embodiments, for example, the heavy hydrocarbon-comprising material has an API (American Petroleum Institute) gravity of less than 20°. In some embodiments, for example, the heavy hydrocarbon-comprising material has an API gravity of less than 15°. In some embodiments, for example, the heavy hydrocarbon-comprising material has an API gravity of less than 12°. In some embodiments, for example, the heavy hydrocarbon-comprising material has an API gravity of less than 10°. In some embodiments, for example, the heavy hydrocarbon-comprising material has an API gravity of less than 5°. In some embodiments, for example, the heavy hydrocarbon-comprising material has an API gravity of less than 0°. In some embodiments, for example, the heavy hydrocarbon-comprising material has an API gravity of less than -2°. In some embodiments, for example, the heavy hydrocarbon-comprising material has an API gravity of less than -4°. In some embodiments, for example, the heavy hydrocarbon-comprising material has an API gravity of less than -8°. In some embodiments, for example, the heavy hydrocarbon-comprising material has an API gravity of less than -10°.

[0036] In some embodiments, for example, the heavy hydrocarbon-comprising material includes, or in some embodiments, consists of, residuum or resid. Exemplary residuum includes various heavy crude and refinery fractions. In this respect, in some embodiments, for example, the heavy hydrocarbon-comprising material includes, or in some embodiments, consists of, fresh resid hydrocarbon feeds, a bottoms stream from any refinery process, such as petroleum atmospheric tower bottoms, vacuum tower bottoms, or a bottoms stream from a coker or a visbreaker or a thermal cracking unit, or a bottoms stream from a FCC or a RFCC unit, hydrocracked atmospheric tower, vacuum tower, FCC, or RFCC bottoms, straight run vacuum gas oil, hydrocracked vacuum gas oil, fluid catalytically cracked (FCC) slurry oils or cycle oils, as well as other similar hydrocarbon-comprising materials, or any combination thereof, each of which may be straight run, process derived, hydrocracked, or otherwise partially treated (for example, desulfurized). The above-described heavy hydrocarbon-comprising material may also include various impurities, such as sulphur, nitrogen, oxygen, halides, and metals.

[0037] In some embodiments, for example, the heavy hydrocarbon-comprising material includes, or in some embodiments, consists of, a crude, such as an heavy and/or an ultra-heavy crude. Crude refers to hydrocarbon material which have been produced and/or retorted from hydrocarbon-containing formations and which has not yet been distilled and/or fractionally distilled in a treatment facility to produce multiple components with specific boiling range distributions, such as atmospheric distillation methods and/or vacuum distillation methods.

Exemplary crudes include coals, bitumen, tar sands, or crude oil. In such embodiments, the crude can be characterized as having a number of separable fractions (or "cuts") that could be separable by distillation, each cut having characterizable properties. In some embodiments, the crude has five cuts: a kerosene fraction, a diesel fraction, a light vacuum gas oil fraction, a heavy vacuum gas oil fraction, and a vacuum residue fraction. In some embodiments, the vacuum residue fraction comprises the asphaltenes.

[0038] In some embodiments, the solvent 106 is a suitable hydrocarbon material which is a liquid at the operating conditions of the solvent material contacting zone. In some embodiments, for example, the solvent is a relatively light hydrocarbon or a mixture including two or more light hydrocarbons. Exemplary light hydrocarbons include propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, nonane, and corresponding mono- olefinic hydrocarbons, and corresponding cyclic hydrocarbons. In some embodiments, for example, the solvent includes one or more paraffinic hydrocarbons having from 3 to 10 carbon atoms in total per molecule. In some embodiments, for example, the solvent is pentane. In some embodiments, the light hydrocarbons include light aromatic hydrocarbons. Exemplary light aromatic hydrocarbons include benzene, and toluene.

[0039] In some embodiments, for example, the solvent 106 is a supercritical fluid at the operating conditions of the contacting zone 103.

[0040] In some embodiments, the operating temperature in the solvent contacting zone is from between about the ambient temperature to about the critical condition of the solvent. In some embodiments, economics will determine the temperature range, even if, theoretically, it may be possible to operate in a significantly wider range. In some embodiments, the upper and lower ends of the operating temperature range is calculated as follows:

[0041] T _max =T _c -0.05 (T _c -T _o ); and

[0042] T| _OW =T _C -0.80 (T _c -T ₀ ).

[0043] In some embodiments, the operating temperature is between about 80 °C and about 200 °C, such as between about 100 °C and about 160 °C.

[0044] In some embodiments, the asphaltenes 104a found in the feed 104 are insoluble in the solvent 106. The contacting of the solvent 106 and the feed 104 causes the asphaltenes 104a found in the feed 104 to precipitate into the asphaltene-rich material fraction 110 while the remainder of the feed 104 is solvated by the solvent 106 to form the deasphalted oil-comprising material fraction 108.

[0045] In some embodiments, for example, the separation in separation zone 109 is effected by gravity separation. In some embodiments, for example, the separation is effected by phase separation. In some embodiments, for example, the separation is effected by extraction. [0046] In some embodiments, the asphaltene-rich material fraction 110, being denser than the deasphalted oil material fraction 108, is recovered as a bottoms product, and the deasphalted oil material fraction is recovered as an overhead product.

[0047] In some of embodiments, for example, both of the contacting zone 103 and the separation zone 109 is effected within a combined contactor/separator, such as a mixer- decanter or in an extraction column. In this respect, the contacting zone 103 and the separation zone 109 are at least partially co-located. Examples of suitable mixers include rotary stirring blades, paddles, or baffles.

[0048] In other embodiments, for example, the deasphalter 101 includes a mixer 103a, the contacting zone 103 defined by the mixer, and the resulting mixture 107 is then supplied to a separator, the separation zone 109 defined by the separator, to effect the gravity separation. In this respect, the contacting zone 103 and the separation zone 109 are separate.

[0049] In some embodiments, the deasphalted oil-comprising material fraction 108 includes substantially all of the solvent 106 and a partially de-asphalted oil, and the asphaltene- rich material fraction 110 includes a pitch and residual solvent.

[0050] In some embodiments, the de-asphalting process is characterized by the following operating parameters:

1. an operating temperature of the contacting;

2. the composition of the feed;

3. the composition of the solvent;

4. a ratio of the mass of the solvent to the mass of the feed ("S/F ratio"); and

5. a ratio of the mass of the precipitated asphaltenes to the mass of the asphaltenes in the feed ("degree of asphaltene separation").

[0051] For example, the operating parameters will affect the properties of the S+PDAO phase at operating conditions. The Rl of the S+PDAO phase can be measured, calculated, or both. In some embodiments, four operating parameters are specified, and a selected operating parameter is controlled based on the Rl of the S+PDAO phase.

[0052] In some embodiments, using the specified operating parameters, the Rl of the

S+PDAO phase is calculated by two methods. In such embodiments, the selected operating parameter is controlled where the Rl values of the S+PDAO phase calculated using the two methods converge. In some embodiments, the selected operating parameter is controlled by obtaining a measured Rl of the S+PDAO phase and using at least one of the two calculation methods.

[0053] A first method ("Method 1") for calculating the Rl of the S+PDAO uses the following equations:

In these equations:

[0054] The values of A ₀ -A ₇ can be determined by fitting data obtained from experimental results. Alternatively or additionally, the values of A ₀ -A ₇ can be determined by calculating Rl's of various feeds, solvents and S+PDAOs, and also the UOP-K factors of various solvents.

[0055] A hydrocarbon, such as a cut the feed 104 or a component of the solvent 106, can be characterized by its Rl. Buckingham, "The Molecular Refraction of an Imperfect Gas" (1956) 52 Transactions of the Faraday Society 747, showed that there is a correlation between Rl and density:

[0056] The hydrocarbon can be further characterized by F _RI , a function of its Rl:

[0057] JS Buckley et al, "Asphaltene Precipitation and Solvent Properties of Crude Oils",

(1998) 16:3-4 Petrol Sci and Tech 251 showed that at ambient conditions and ideal volume of mixing, the F _ra of a mixture can be calculated based on its components as follows:

[0058] FM Vargas and WG Chapman, "Application of the One-Third Rules in

Hydrocarbon and Crude Oil Systems", (2010) 290:1 Fluid Phase Equilibria 103 showed a formula for extrapolating the Rl of a hydrocarbon at a temperature T, based on the Rl and density of the hydrocarbon at a reference temperature and the density of the hydrocarbon at the temperature T:

[0059] A hydrocarbon, such as a light hydrocarbon, can be characterized by a UOP-K characterization factor. The UOP-K characterization factor can be calculated using the method set out in KM Watson and EF Nelson, "Improved Methods for Approximating Critical and Thermal Properties of Petroleum Fractions", 1933 85 ^th Meeting of the American Chemical Society: Symposium on Physical Properties of Hydrocarbon Mixtures:

[0060] In embodiments where the solvent 106 includes more than one hydrocarbon, the

UOP-K characterization of the solvent can be calculated as a weighted aggregate of the UOP-K characterization factor of each hydrocarbon according to: where:

w,: mass fraction of hydrocarbon, i, in the solvent; and

UOP-K,: UOP-K characterization factor of the hydrocarbon.

[0061] A second method for calculating the Rl of the S+PDAO at the operating temperature uses mass balances and the correlations described in equations (4)-(7) ("Method 2").

[0062] In embodiments where Rl is calculated using Method 1 and Method 2, an initial value is specified for the selected operating parameter. The initial value is used to calculate the Rl of the S+PDAO at the operating temperature using Method 2. The convergence of the Rl of the S+PDAO at the operating temperature calculated using Method 1 and Method 2 indicates that the value of the selected operating parameter used in the calculation of Method 2 is the value that should be used in the solvent de-asphalting process. If the values of the Rl of the S+PDAO at the operating temperature calculated using Method 1 and Method 2 do not converge, a new value of the selected operating parameter is specified and the Rl of the S+PDAO at the operating temperature is re-calculated using Method 2. This calculation can be iterated with new values of the selected operating parameter until the values Rl of the S+PDAO at the operating temperature calculated using Method 1 and Method 2 converge.

[0063] In some embodiments, the de-asphalting system 100 includes a flow regulator

114 operatively connected to the controller 112 for controlling a flow feed rate of the feed 104, a solvent feed rate of the solvent 106, or both.

[0064] In some embodiments, the de-asphalting system 100 includes a temperature regulator 116 operatively connected to the controller 112 for controlling the operating temperature. In some embodiments, the temperature regulator is a heater 111. Examples of suitable heaters include heat exchangers, furnaces, or boilers.

[0065] In some embodiments, the de-asphalting system 100 includes a pre-heater (not shown) upstream of the deasphalter 101 for pre-heating the feed 104, the solvent 106 or both. [0066] In some embodiments, the de-asphalting system 100 includes an Rl determining device 117 operatively connected to the controller 112 for determining the Rl of the S+PDAO 108. In some embodiments, the Rl determining device is a refractometer for measuring the Rl of the S+PDAO 108. In some embodiments, the Rl determining device is a densitometer for measuring the density of the S+PDAO to determine the Rl of the S+PDAO, for example, by using the correlation set out in equation (4).

[0067] In some embodiments, the de-asphalting system 100 includes a secondary de- asphalter (not shown) for removing at least a portion of the asphaltenes present in the S+PDAO phase 108.

[0068] In some embodiments, the de-asphalting system 100 includes a S+PDAO separator (not shown) for separating the S+PDAO 108 to obtain a S+PDAO-derived solvent. In such embodiments, the solvent 106 includes at least a portion of the S+PDAO-derived solvent.

[0069] In some embodiments, the de-asphalting system 100 includes a pitch stripper

(not shown) for separating the asphaltene-rich material fraction 110 to obtain a pitch-derived solvent. In such embodiments, the solvent 106 comprises at least a portion of the pitch-derived solvent.

[0070] In another aspect, there is provided a method for solvent deaspalting 200 (Figure

2). At block 202, a feed, including asphaltenes, at a feed flow rate is provided. At block 204, a solvent at a solvent flow rate is provided. At block 206, the feed and the solvent are contacted to effect precipitation of at least a portion of the asphaltenes to obtain a S+PDAO and an asphaltene-rich material fraction. The asphaltene-rich material fraction, includes the precipitated asphaltenes. The contacting is disposed of at an operating temperature. At block 208, at least one operating parameter is controlled based on at least a refractive index of the S+PDAO, the operating parameter is selected from: the operating temperature; the composition of the feed; the composition of the solvent; a ratio of the precipitated asphaltenes to the mass of asphaltenes within the feed; and a ratio of the feed flow rate to the solvent flow rate.

[0071] In another aspect, there is provided a deasphalted oil obtained by a method 300

(Figure 3). At block 302, a feed, including asphaltenes, at a feed flow rate is provided. At block 304, a solvent at a solvent flow rate is provided. At block 306, the feed and the solvent are contacted to effect precipitation of at least a portion of the asphaltenes to obtain a S+PDAO and an asphaltene-rich material fraction. The asphaltene-rich material fraction, includes the precipitated asphaltenes. The contacting is disposed of at an operating temperature. At block 308, at least one operating parameter is controlled based on at least a refractive index of the S+PDAO, the operating parameter is selected from: the operating temperature; the composition of the feed; the composition of the solvent; a ratio of the precipitated asphaltenes to the mass of asphaltenes within the feed; and a ratio of the feed flow rate to the solvent flow rate.

[0072] In another aspect, there is provided a method for solvent de-asphalting 400

(Figure 4). At block 402, operating parameters of the de-asphalting are defined, the operating parameters including: a composition of a feed, including asphaltenes; a target ratio of a mass of removed asphaltenes to the mass of asphaltenes within the feed; an operating temperature for contacting the feed and a solvent; and a ratio of a feed flow rate of the feed to a solvent flow rate of the solvent. At block 404, an Rl of the solvent is determined based at least on calculating the Rl of an S+PDAO formed by contacting the feed with the solvent. At block 406, a solvent is selected based at least on the solvent Rl determined at block 404. At block 408, the solvent selected in block 406 is contacted with the feed at the operating parameters defined at block 402 to effect de-asphalting.

[0073] In another aspect, there is provided a method for solvent de-asphalting 500

(Figure 5). At block 502, a solvent is selected based on Rl. At block 504, the selected solvent is contacted with a feed including asphaltenes to effect de-asphalting.

[0074] In another aspect, there is provided a method for starting up a solvent deasphalting process 600 (Figure 6). At block 602, four operating parameters are set at predetermined values, the operating parameters are selected from: an operating temperature; a composition of a feed; a composition of a solvent; a target ratio of a mass of precipitated asphaltenes to a mass of asphaltenes initially within the feed; and a ratio of a feed flow rate to a solvent flow rate. At block 604, the non-predetermined operating parameter is determined based on an expected Rl of an S+PDAO stream generated by the process. At block 606, the process is started up using the pre-determined operating parameters and the determined operating parameter.

[0075] Other features and embodiments of the invention will become apparent from the following examples which are given for illustration of the invention rather than for limiting its intended scope. Examples

[0076] In the following illustrative examples, a S/F ratio for a solvent de-asphalting process is controlled.

Example 1 : Defining Process variables

[0077] In this example, the S/F ratio is controlled at a first stage de-asphalting operation.

[0078] The following four operating parameters are selected:

1. the operating temperature;

2. the feed composition;

3. the solvent composition; and

4. the degree of asphaltene separation.

[0079] 1 ) Temperature: In this example, the operating temperature is 165°C.

[0080] 2) Feed composition:

[0081] In this example, the feed composition is bitumen. Bitumen is a mixture of components and can be characterized as having five fractions (or "cuts"): a kerosene fraction, a diesel fraction, a light vacuum gas oil fraction, a heavy vacuum gas oil fraction, and a vacuum residue fraction.

[0082] In this example, the bitumen has the following composition:

Table 1 : Feed composition

[0083] The bitumen of this example includes asphaltene having the following properties:

Table 2:

[0084] 3) Solvent composition:

[0085] The solvent can be one or more solvents. In this example, the solvent has the following composition:

Table 3: Solvent composition

Note:

'Nonanes+' density/boiling point were approximated with Decane density/boiling point.

'Cyclopentane & Methylcyclopentane' density/boiling point were approximated with Cyclopentane density/boiling point.

'Cyclohexane & Methylcyclohexane' density/boiling point were approximated with Cyclohexane density/boiling point.

'Aromatics C7+' density/boiling point were approximated with Toluene density/boiling point. [0086] In this example, the solvent has the following properties:

[0087] Table 4: Solvent density

[0088] 4) The degree of asphaltene separation:

[0089] In this example, the degree of asphaltene separation is 50%, i.e. half of the asphaltenes of the bitumen will be precipitated. Asphaltenes are those compounds that are not soluble in solvent. It is assumed that these are the only insoluble compounds in the feed. As such, it is assumed that the pitch will consist only of asphaltenes.

Example 2: Calculating using developed equations:

[0090] As noted above, the Rl of the S+PDAO can be calculated using Method 1 with the following equations:

[0091] The values of A ₀ -A ₇ are determined by fitting data obtained from experimental results.

[0092] First, the Rl of the feed and solvent at the operating temperature are calculated

(see Ex 2.1 and 2.2, below)

[0093] Second, the Rl of the S+PDAO at the extraction temperature

is calculated literature correlations (see Ex 3.3, below)

[0094] Third, the Rl of the S+PDAO at the extraction temperature ' ^S

calculated using experimental results (see Ex 2.4)

[0095] Lastly, the coefficients A ₀ - A ₇ are tuned to minimize the difference between the

Rl of the S+PDAO at the extraction temperature calculated in the second and third steps.

[0096] Using this method, it is determined that there are three possible sets of values for

A ₀ -A ₇ : 1 ) a first stage de-asphalting operation operating at temperatures >120°C; 2) a first stage de-asphalting operation operating at temperatures <100°C; and 3) a second stage de- asphalting operation as set out below:

[0097] Table 5.

[0098] Based on equations (1 )-(3), it is seen that

are determined before solving for These are calculated in Examples 2.1 , 2.2 and 2.3, respectively. The ' ^s calculated in Example 2.4.

Example 2.1 : Calculate

Example 2.1.1 : Calculate Rl of each component fractions of the feed

[0099] Recall equation (4) above:

[00100] The virial coefficients, A, B and C, are determined using fitting and data analysis for a variety of hydrocarbon compounds. These are determined to be 0.4597, -0.2425, and 0.1134, respectively.

[00101] Equation (4) is modified to solve for Rl with a known density:

[00102] Equation (10) is used to calculate the Rl of each cut:

[00103] The results are shown below (densities from Table 1 , above): Light Vacuum Gas Oil 937.64 1.5350

Heavy Vacuum Gas Oil 979.38 1.5617

Vacuum Residue 1 ,086.01 1.6378

Example 2.1.2: Calculate FRI, a function refractive index, for each cut

[00104] Recall equation (5), above:

[00105] Equation (5) is modified to calculate the F _RI of each fraction:

[00106] The results are shown below (densities from Table 1 , above):

Example 2.1.3: Calculate F _RI for the entire feed:

[00107] Recall equation (6), above:

[00108] Equation (6) is used to calculate the FRI of the feed composition:

[00109] Recall:

Note: Volume fractions from Table 1

[00110] Solving for

Example 2.1.4: Calculate Rl for the entire feed:

[00111] Recall equation (5):

[00112] Equation (5) is re-arranged to solve for the Rl:

Equation (11) can be used to solve for the Rl of the Feed 25°C: [00114] Solving for

Example 2.1.5 Calculate Rl at the operating temperature:

[00115] Recall equation (7):

[00116] Equation (7) is rearranged to solve for the Rl of a new temperature given a reference temperature of 25°C:

[00117] Recall (from Table 1 ):

[00118] Solving for Rl of the feed at the operating temperature:

Example 2.2: Calculate (using same method as the feed):

[00119]

Example 2.3: Calculate

Example 2.3.1: Calculate UOP-K for each component in the solvent:

[00120] Recall equation (8):

[00121] Solving for each component of the solvent (using density and boiling point from Table 3, above):

Example 2.3.2: Calculate UOP-K for the combined solvent

[00122] Recall equation (9) [00123] Using the weight fractions from Table 2 and the UOP-K's calculated in the previous step:

Example 2.4: Calculate Rl of the S+PDAO at 165°C using Method 1:

[00124] Recall:

The degree of asphaltene separation is selected to be 0.5 (Ex. 1 )

The values of A ₀ -A ₇ are found in Table 1 , using the values for stage 1 and temperatures of above 120°C.

The values of were calculated above (Ex 2.1 , 2.2, and 2.3)

[00125] Example 2.4.1 calculate

[00126] Solve for using equation (2):

Example 2.4.2 calculate slope [00127] Solve for slope using equation (3)

Example 2.4.2 calculate

[00128] Solve for using equation (1 ):

Example 3: Calculating using correlations from the literature and mass balances.

[00129] The is calculated using correlations from the literature and mass

balances (Method 2). This calculated value will be compared to the calculated in Ex 2 using Method 1. The convergence of these values is used to control the S/F ratio (Ex 4).

[00130] Equation (12) is re-arranged to solve for Rl of the S+PDAO:

[00131] The values of are calculated first

(Ex 3.2, 3.3) before calculating

Example 3.1 Guess the S/F ratio:

[00132] The S/F ratio is the operational parameter being controlled (see Ex 1 ). This value will affect the equilibrium of the streams (e.g. the densities of the pitch and S+PDAO will be affected).

[00133] Start with an initial guess for the S/F ratio. In this example, the initial guess is:

S/F=1.20

Where

S/F: S/F Ratio (on weight basis).

Example 3.1.1 Calculate the weight % (on Feed basis) of Solvent:

[00134] By applying a mass balance:

[00135] Solving:

Example 3.2 Calculate

Example 3.2.1 Calculate the density of the pitch:

[00136] Recall from Ex. 1 , that the pitch consists of C5-asphaltenes. It follows that the density of the pitch is equal to the density of the C5-asphaltenes:

[00137] Recall from Table 2:

Example 3.2.2 Calculate the weight % (on Feed basis) of Pitch:

[00138] Since the pitch is the portion of the C5-asphaltenes removed from the feed:

[00139] Solving for w _Pitch : [00140] Since the partially de-asphalted oil will be the portion of the feed after the removal of the pitch:

[00141] Solving:

Example 3.2.4 Calculate the density of the PDAO:

[00142] The density of the partially de-asphalted oil can be calculated as follows:

[00143] Solving for density at 25°C and operating temperature (165°C):

Example 3.2.5 Calculating the weight of the solvent in the pitch+solvent phase

[00144] Based on experimental data, the weight fraction of solvent in the Pitch+Solvent, after phase separation is determined to be correlated with the density of pitch at the extraction temperature according to the following formula:

[00145] Solving for

Example 3.2.6 the weight % (on Feed basis) of Pitch+S:

[00146] By applying a mass balance:

[00147] Solving:

Example 3.2.7 calculate the density of the Pitch+Solvent:

[00148] The density of the pitch-solvent can be calculated as follows:

[00149] Solving:

Example 3.2.8 Calculate the weight % (on Feed basis) of the S+PDAO:

The weight of the S+PDAO phase can be calculated by a mass balance:

[00150] Solving:

Example 3.2.9 Calculate the density of the S+PDAO at 25°C and at the extraction temperature:

The density of the S+PDAO phase

[00151] Solving for density of the S+PDAO at a reference temperature and the operating temperature:

Example 3.3 Calculate

Example 3.3.1 the volume % of Pitch (on Feed basis) at 25°C:

[00152] Solving:

Example 3.3.2 Calculate the volume % of Solvent (on Feed basis) at 25°C:

[00153] The volume of solvent can be calculated as follows:

[00154]

[00155] Solving:

Example 3.3.3 Calculate the volume % of Pitch+S (on Feed basis) at 25°C:

[00156] The volume of pitch-solvent can be calculated as follows:

[00157] Solving:

Example 3.3.4 the volume % of PDAO (on Feed basis) at 25°C:

[00158] The volume % of PDAO (on Feed basis) at 25°C is calculated via a mass balance:

[00159] Solving:

Example 3.3.5 Calculate the volume % of S+PDAO (on Feed basis) at 25°C:

[00160] The volume of S+PDAO (on feed basis) at 25°C is calculated via a mass balance:

[00161] Solving:

Volume % of S+PDAO (on Feed basis) at 25°C

Example 3.3.6 Calculate RI of pitch:

[00162] Equation (10) is used to calculate the RI of pitch @ 25°C:

[00163] Solving:

Example 3.3.7 Calculate F _RI of pitch:

Example 3.3.8 Calculate the F _RI of the PDAO at 25°C:

[00166] Recall equation (6) and solving for F _RI of the partially deasphalted oil: [00167] Solving:

Example 3.3.9 Calculate F _RI of the S+PDAO at 25°C:

[00168] Re-arranging equation (6):

[00169] Solving:

FRI of the S+PDAO at 25°C:

Example 3.3.10 Calculate the Rl of the S+PDAO at 25°C:

Equation (11 ) from Ex 2.1.4 is used to solve the for

Where:

[00170] Solving:

Rl of the S+PDAO at 25°C

Example 3.3.11 calculate the Rl of the S+PDAO at the extraction temperature:

[00171] Equation (12) from Ex 2.1.5 can be used to calculate

[00172] Solving:

Example 4 Check whether the two methods of calculating the Rl of S+PDAO at the extraction temperature have converged:

[00173] Recall, the Rl of the S+PDAO calculated in Ex 2 and 3 are:

[00174] Since Ex 3 is iterated using new

guesses until the Rl values converge.

[00175] the guessed S/F Ratio in Ex 3

is decreased.

[00176] the guessed S/F Ratio in Ex 3

is increased.

[00177] The guessed value of the selected operating parameter at the convergence of the Rl values calculated using Method 1 and Method 2 is the controlled value of the selected operating parameter.

[00178] The above description is meant to be exemplary only, and one skilled in the relevant arts will recognize that changes may be made to the embodiments described without departing from the scope of the disclosure. For example, the operations represented in the drawing described herein are for purposes of example only. There may be many variations to these operations without departing from the teachings of the present disclosure. For instance, the operations may be performed in a differing order, or operations may be added, deleted, or modified. The present disclosure may be embodied in other specific forms without departing from the subject matter of the claims. Also, one skilled in the relevant arts will appreciate that while the systems, devices and assemblies disclosed and shown herein may comprise a specific number of elements/components, the systems, devices and assemblies could be modified to include additional or fewer of such elements/components. The present disclosure is also intended to cover and embrace all suitable changes in technology. Modifications which fall within the scope of the present invention will be apparent to those skilled in the art, in light of a review of this disclosure, and such modifications are intended to fall within the scope of the appended claims. [00179] Every document, including publications and published patent documents, cited herein is hereby incorporated herein by reference in its entirety. The citation of any document is not an admission that it is prior art with respect to the present disclosure. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.