CA3092096C - Method and system for reducing olefin content of partially upgraded bitumen - Google Patents
Method and system for reducing olefin content of partially upgraded bitumen Download PDFInfo
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Abstract
Systems and methods are provided for partial upgrading of bitumen (and/or other heavy hydrocarbon feeds) while reducing or minimizing the hydrogen consumption associated with the partial upgrading. The partial upgrading of the bitumen can correspond to any convenient type of catalytic and/or thermal upgrading. After the partial upgrading, a naphtha and/or distillate boiling range portion of the thermally upgraded effluent can be passed into a catalytic reformer. The reformer can be operated under conditions that are suitable for olefin saturation in addition to some aromatic formation. The resulting naphtha and distillate portions of the reformer effluent, having a reduced or minimized content of olefins, can be combined with one or more additional portions of the partially upgraded effluent to form a partially upgraded product.
Description
METHOD AND SYSTEM FOR REDUCING OLEFIN CONTENT
OF PARTIALLY UPGRADED BITUMEN
[0001] FIELD
OF PARTIALLY UPGRADED BITUMEN
[0001] FIELD
[0002] Systems and methods are provided for reducing or minimizing the olefin content of partially upgraded crude oils.
BACKGROUND
BACKGROUND
[0003] Oil sands are a type of non-traditional petroleum source that remains challenging to fully exploit. Due to the nature of oil sands, substantial processing can be required at or near the extraction site just to create bitumen / crude oil fractions that are suitable for transport. However, oil sands extraction sites are also often in geographically remote locations, which can substantially increase the construction and maintenance costs for any processing equipment that is used at the oil sands site.
[0004] Some options for preparing bitumen for transport can involve thermal and/or catalytic upgrading of at least a portion of the feed. This can include processes such as visbreaking, coking, or various types of hydroprocessing. While such thermal and/or catalytic upgrading of bitumen can be effective for improving the properties of the at least partially upgraded bitumen, the upgrading can also produce additional olefins at levels that are problematic for some types of transport. As a result, thermal and/or catalytic upgrading of bitumen is often conventionally paired with a hydrotreatment stage, so that olefin content generated during upgrading can be reduced to a desirable level. However, such hydrotreating requires a source of hydrogen, which can be difficult and/or expensive to provide at a bitumen upgrading site.
[0005] What is needed are improved systems and methods for thermal and/or catalytic upgrading of bitumen that produce an at least partially upgraded bitumen with a low olefin content while reducing or minimizing the need to transport additional hydrogen to the upgrading site.
Date Recue/Date Received 2022-02-02 100061 U.S. Patents 5,011805 and 4,935,566 describe methods for performing catalytic reforming on naphtha boiling range feeds to produce higher octane gasoline and/or increased amounts of aromatics.
100071 U.S. Patent 6,602,404 describes an example of catalytic reforming. A
naphtha and kerosene boiling range feed to separate out a heavy naphtha portion. The heavy naphtha portion is reformed to produce aromatics with increased selectivity for formation of xylenes. Other examples of catalytic reforming processes include U.S. Patents 5,011,805 and 4,935,566.
100081 U.S. Patent 8,845,884 describes reforming a naphtha feed by splitting the naphtha into a light portion and heavy portion. The light portion and heavy portion are reformed under different conditions to allow for improved formation of C6 ¨ C8 aromatics in each portion.
100091 U.S. Patent 4,615,791 describes an example of visbreaking of a resid feedstock in the presence of a hydrogen donor solvent.
SUMMARY
100101 In an aspect, a method for upgrading a heavy hydrocarbon feed is provided. The method can include exposing a heavy hydrocarbon feedstock comprising an API gravity of 16 or less and kinematic viscosity at 7.5 C of 500 cSt or more to a partial upgrading process to form a partially processed effluent. The partially processed effluent can include 1.1 wt% or more of olefins, or 2.0 wt% or more. The method can further include separating, from the partially processed effluent, a first fraction and a second fraction. The first fraction can have a T95 distillation point of 750 F
(400 C) or less, and the second fraction can have a higher T95 distillation point than the first fraction. The first fraction can further include a weight percentage of olefins that is greater than the weight percentage of olefins in the partially processed effluent. The method further includes exposing at least a portion of the first fraction to a reforming process to form at least a reformed fraction and a hydrogen-containing fraction. The reformed fraction can include less than 1.0 wt%
olefins. Additionally, the method can include blending at least a portion of the reformed fraction with the second fraction to form a partially upgraded product. The partially upgraded product can include an API gravity of 14 or more and a kinematic viscosity at 7.5 cSt of 500 cSt or less.
Optionally, the heavy hydrocarbon feedstock can correspond to a bitumen.
100111 In another aspect, a method for upgrading a feedstock is provided.
The method includes separating an initial feedstock comprising an API gravity of 16 or less and a kinematic viscosity at Date Recue/Date Received 2020-09-03 7.5 C of 500 cSt or more to form at least a light feedstock fraction and a heavy feedstock fraction.
The light feedstock fraction can have a T95 distillation point of 500 C or less and/or the heavy feedstock fraction can have a T50 distillation point greater than 500 C. The method further includes exposing at least a portion of the heavy feedstock fraction to a partial upgrading process to form a partially processed effluent. The partially processed effluent can include 1.1 wt% or more of olefins.
The method can further include separating, from the partially processed effluent, a first fraction and a second fraction. The first fraction can have a T95 distillation point of 750 F (-400 C) or less and the second fraction can have a higher T95 distillation point than the first fraction. The first fraction can further include a weight percentage of olefins that is greater than the weight percentage of olefins in the partially processed effluent. The method can further include exposing at least a portion of the first fraction and at least a portion of the light feedstock fraction to a reforming process to form at least a reformed fraction and a hydrogen-containing fraction. The reformed fraction can include less than 1.0 wt% olefins. Additionally, the method can include blending at least a portion of the reformed fraction with the second fraction to form a partially upgraded product. The partially upgraded product can include an API gravity of 14 or more and a kinematic viscosity at 7.5 cSt of 500 cSt or less. Optionally, the T95 distillation point of the light feedstock fraction can be 400 C or less. Optionally, the initial feedstock can correspond to a bitumen feedstock.
BRIEF DESCRIPTION OF THE DRAWING
100121 Figure 1 shows an example of a configuration for upgrading a heavy hydrocarbon feed, such as a bitumen feed.
DETAILED DESCRIPTION
100131 All numerical values within the detailed description and the claims herein are modified by "about" or "approximately" the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.
Overview 100141 In various aspects, systems and methods are provided for partial upgrading of bitumen (and/or other heavy hydrocarbon feeds) while reducing or minimizing the hydrogen consumption associated with the partial upgrading. The partial upgrading of the bitumen can correspond to any convenient type of catalytic and/or thermal upgrading. After the partial upgrading, a naphtha and/or distillate boiling range portion of the thermally upgraded effluent can be passed into a catalytic Date Recue/Date Received 2020-09-03 reformer. The reformer can be operated under conditions that are suitable for olefin saturation in addition to some aromatic formation. The resulting naphtha and distillate portions of the reformer effluent, having a reduced or minimized content of olefins, can be combined with one or more additional portions of the partially upgraded effluent to form a partially upgraded product.
100151 Thermal and/or catalytic methods of partial upgrading typically result in formation of olefins in the partially upgraded effluent, such as having an olefin content of 1.1 wt% or more, or 2.0 wt% or more. The olefins generated during partial upgrading are typically concentrated in the naphtha and distillate boiling range portions of the partially upgraded effluent. When visbreaking is used for partial upgrading, the naphtha fraction of the partially upgraded effluent can generally have an olefin content of about 5.0 wt% to 15 wt%, while the distillate fraction can have an olefin content of about 1.0 wt% to 6.0 wt%. The vacuum gas oil and resid portions of the partially upgraded effluent can tend to have olefin contents that are low enough that separate olefin saturation is not necessary. For example, the olefins in the naphtha, distillate, and vacuum gas oil fractions of partially upgraded bitumens were characterized using hydrogen nuclear magnetic resonance spectroscopy (1-1-NMR). The partial upgrading was performed by visbreaking.
The naphtha fractions included between 8.0 wt% to 10 wt% olefins. The distillate fractions included up to 1.5 wt% olefins. The vacuum gas oil and fractions included up to 1.0 wt% olefins.
100161 Based on the above olefin contents, some type of treatment to reduce olefin content is necessary in order to achieve an olefin content of less than 1.0 wt% for the overall partially upgraded bitumen product composition in order to meet pipeline specifications. Because the distillate fraction can also include more than 1.0 wt% olefins, in some aspects it is desirable to treat both the naphtha and the distillate fractions. Optionally, a portion of the vacuum gas oil fraction could also be treated.
While hydrotreatment (such as fixed bed or trickle bed hydrotreatment) can be effective for saturating such olefins, performing hydrotreatment requires a separate source of hydrogen. At a remote site, excess hydrogen is typically not readily available from other processes.
100171 Instead of performing hydrotreatment, in various aspects of the present disclosure, a catalytic reforming stage can be used to saturate olefins within the naphtha and/or distillate boiling range portions of the partially upgraded bitumen. In addition to forming aromatics, it has been discovered that catalytic reforming can be used to saturate olefins within the naphtha and distillate fractions of a partially upgraded bitumen. Rather than requiring an external source of hydrogen, Date Recue/Date Received 2020-09-03 catalytic reforming provides a method for saturating olefins and/or converting within the naphtha and/or distillate fractions while producing excess hydrogen. Without being bound by any particular theory, it is believed that olefins can be converted to aromatic ring structures under the conditions of a reforming process. Additionally, it is believed that the olefins can be saturated "in-situ" by H2 generated in the reforming environment. This hydrogen is generated as aromatics are formed from naphthenes and/or as olefins are formed from paraffins within the catalytic reforming process.
100181 Using a reforming stage instead of a hydrotreatment stage for olefin reduction can allow for other integration opportunities. For example, the hydrogen generated by reforming can be used to provide hydrogen to the partial upgrading process, when the partial upgrading corresponds to sodium desulfurization, visbreaking in the presence of hydrogen and/or a hydrogen donor solvent, or some type of hydroprocessing. As another example, any light ends (C4_) compounds generated during reforming can be used as fuel gas to provide heat for the partial upgrading process.
100191 Still a further advantage of using reforming instead of hydrotreatment for olefin saturation is that the reformed naphtha and distillate fractions can have an increased content of aromatics. This can increase the solvency of the naphtha and distillate fractions, thus potentially reducing the amount of upgrading that is needed to achieve a desired set of transport properties.
100201 Yet another potential advantage is that the reforming stage may provide a further viscosity reduction for the portions of the partially upgraded effluent that are exposed to the reforming conditions. In some aspects, the kinematic viscosity at 7.5 C for the partially upgraded product can be lower than the kinematic viscosity at 7.5 C for the partial upgrading effluent by 10 cSt or more.
Definitions 100211 In this discussion, the relative severity of visbreaking processes can be compared by referring to a severity index. Severity (or severity index, SI) is a function of reaction time and temperature used during visbreaking. It provides an indication of the severity of the reaction and can be used to compare results of reactions carried out at different conditions. The severity index is defined as:
(1) S/ = t exp[¨ ¨RE (¨T1 ¨ ¨7010)1 100221 In Equation (1), t is the reaction time in seconds, E is the activation energy associated with bitumen thermal cracking, R is the universal gas constant and T is the reaction temperature.
Date Recue/Date Received 2020-09-03 The severity index equals the time required in seconds at 427 C (700 K) to achieve the same degree of reaction (e.g. pitch conversion). For conversion of bitumen, E can generally be set to a value between 50 kcal/mol to 55 kcal/mol.
100231 In this discussion, a hydrogen donor solvent refers to a solvent that can be added to bitumen during processing to allow for higher severity while reducing or minimizing coking. The hydrogen donor solvent can have a higher hydrogen to carbon ratio (i.e., a higher hydrogen content) than the bitumen. For bitumen processing, a recycle fraction from a partially upgraded effluent, such as a recycled naphtha, distillate and/or vacuum gas oil fraction, can be a suitable hydrogen donor solvent. In some aspects, it is noted that addition of a hydrogen donor solvent can potentially provide an additional benefit by acting as a diluent for the feed. This can improve flow properties, such as kinematic viscosity and/or density, which could facilitate cracking.
100241 In this discussion, a fuel gas is defined as a fraction that includes a sufficient amount of Ci ¨ C4 components to be suitable for combustion as a fuel, such as about 5.0 vol% or more of Ci ¨
C4 components, or 10 vol% or more, or 20 vol% or more. Fuel gas can optionally include a variety of other components, such as nitrogen, carbon dioxide, water, and/or other typical components of air; other fuel components such as hydrogen or carbon monoxide; and/or other components that are gases at 25 C and 100 kPa-a.
100251 In this discussion, unless otherwise specified, "conversion" of a feedstock or other input stream is defined as conversion relative to a conversion temperature of 566 C
(1050 F). Once-through conversion refers to the amount of conversion that occurs during a single pass through a reactor / stage / reaction system. Total conversion refers to the net products from the reactor / stage / reaction system, so that any recycle streams are included in the calculation of the total conversion.
It is noted that in all aspects described herein, the amount of conversion at 524 C is lower than the corresponding conversion at 566 C.
100261 In this discussion, a "Cx" hydrocarbon refers to a hydrocarbon compound that includes "x" number of carbons in the compound. A stream containing "Cx ¨ Cy"
hydrocarbons refers to a stream composed of one or more hydrocarbon compounds that includes at least "x" carbons and no more than "y" carbons in the compound. It is noted that a stream comprising G
¨ Cy hydrocarbons may also include other types of hydrocarbons, unless otherwise specified.
Date Recue/Date Received 2022-02-02 100061 U.S. Patents 5,011805 and 4,935,566 describe methods for performing catalytic reforming on naphtha boiling range feeds to produce higher octane gasoline and/or increased amounts of aromatics.
100071 U.S. Patent 6,602,404 describes an example of catalytic reforming. A
naphtha and kerosene boiling range feed to separate out a heavy naphtha portion. The heavy naphtha portion is reformed to produce aromatics with increased selectivity for formation of xylenes. Other examples of catalytic reforming processes include U.S. Patents 5,011,805 and 4,935,566.
100081 U.S. Patent 8,845,884 describes reforming a naphtha feed by splitting the naphtha into a light portion and heavy portion. The light portion and heavy portion are reformed under different conditions to allow for improved formation of C6 ¨ C8 aromatics in each portion.
100091 U.S. Patent 4,615,791 describes an example of visbreaking of a resid feedstock in the presence of a hydrogen donor solvent.
SUMMARY
100101 In an aspect, a method for upgrading a heavy hydrocarbon feed is provided. The method can include exposing a heavy hydrocarbon feedstock comprising an API gravity of 16 or less and kinematic viscosity at 7.5 C of 500 cSt or more to a partial upgrading process to form a partially processed effluent. The partially processed effluent can include 1.1 wt% or more of olefins, or 2.0 wt% or more. The method can further include separating, from the partially processed effluent, a first fraction and a second fraction. The first fraction can have a T95 distillation point of 750 F
(400 C) or less, and the second fraction can have a higher T95 distillation point than the first fraction. The first fraction can further include a weight percentage of olefins that is greater than the weight percentage of olefins in the partially processed effluent. The method further includes exposing at least a portion of the first fraction to a reforming process to form at least a reformed fraction and a hydrogen-containing fraction. The reformed fraction can include less than 1.0 wt%
olefins. Additionally, the method can include blending at least a portion of the reformed fraction with the second fraction to form a partially upgraded product. The partially upgraded product can include an API gravity of 14 or more and a kinematic viscosity at 7.5 cSt of 500 cSt or less.
Optionally, the heavy hydrocarbon feedstock can correspond to a bitumen.
100111 In another aspect, a method for upgrading a feedstock is provided.
The method includes separating an initial feedstock comprising an API gravity of 16 or less and a kinematic viscosity at Date Recue/Date Received 2020-09-03 7.5 C of 500 cSt or more to form at least a light feedstock fraction and a heavy feedstock fraction.
The light feedstock fraction can have a T95 distillation point of 500 C or less and/or the heavy feedstock fraction can have a T50 distillation point greater than 500 C. The method further includes exposing at least a portion of the heavy feedstock fraction to a partial upgrading process to form a partially processed effluent. The partially processed effluent can include 1.1 wt% or more of olefins.
The method can further include separating, from the partially processed effluent, a first fraction and a second fraction. The first fraction can have a T95 distillation point of 750 F (-400 C) or less and the second fraction can have a higher T95 distillation point than the first fraction. The first fraction can further include a weight percentage of olefins that is greater than the weight percentage of olefins in the partially processed effluent. The method can further include exposing at least a portion of the first fraction and at least a portion of the light feedstock fraction to a reforming process to form at least a reformed fraction and a hydrogen-containing fraction. The reformed fraction can include less than 1.0 wt% olefins. Additionally, the method can include blending at least a portion of the reformed fraction with the second fraction to form a partially upgraded product. The partially upgraded product can include an API gravity of 14 or more and a kinematic viscosity at 7.5 cSt of 500 cSt or less. Optionally, the T95 distillation point of the light feedstock fraction can be 400 C or less. Optionally, the initial feedstock can correspond to a bitumen feedstock.
BRIEF DESCRIPTION OF THE DRAWING
100121 Figure 1 shows an example of a configuration for upgrading a heavy hydrocarbon feed, such as a bitumen feed.
DETAILED DESCRIPTION
100131 All numerical values within the detailed description and the claims herein are modified by "about" or "approximately" the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.
Overview 100141 In various aspects, systems and methods are provided for partial upgrading of bitumen (and/or other heavy hydrocarbon feeds) while reducing or minimizing the hydrogen consumption associated with the partial upgrading. The partial upgrading of the bitumen can correspond to any convenient type of catalytic and/or thermal upgrading. After the partial upgrading, a naphtha and/or distillate boiling range portion of the thermally upgraded effluent can be passed into a catalytic Date Recue/Date Received 2020-09-03 reformer. The reformer can be operated under conditions that are suitable for olefin saturation in addition to some aromatic formation. The resulting naphtha and distillate portions of the reformer effluent, having a reduced or minimized content of olefins, can be combined with one or more additional portions of the partially upgraded effluent to form a partially upgraded product.
100151 Thermal and/or catalytic methods of partial upgrading typically result in formation of olefins in the partially upgraded effluent, such as having an olefin content of 1.1 wt% or more, or 2.0 wt% or more. The olefins generated during partial upgrading are typically concentrated in the naphtha and distillate boiling range portions of the partially upgraded effluent. When visbreaking is used for partial upgrading, the naphtha fraction of the partially upgraded effluent can generally have an olefin content of about 5.0 wt% to 15 wt%, while the distillate fraction can have an olefin content of about 1.0 wt% to 6.0 wt%. The vacuum gas oil and resid portions of the partially upgraded effluent can tend to have olefin contents that are low enough that separate olefin saturation is not necessary. For example, the olefins in the naphtha, distillate, and vacuum gas oil fractions of partially upgraded bitumens were characterized using hydrogen nuclear magnetic resonance spectroscopy (1-1-NMR). The partial upgrading was performed by visbreaking.
The naphtha fractions included between 8.0 wt% to 10 wt% olefins. The distillate fractions included up to 1.5 wt% olefins. The vacuum gas oil and fractions included up to 1.0 wt% olefins.
100161 Based on the above olefin contents, some type of treatment to reduce olefin content is necessary in order to achieve an olefin content of less than 1.0 wt% for the overall partially upgraded bitumen product composition in order to meet pipeline specifications. Because the distillate fraction can also include more than 1.0 wt% olefins, in some aspects it is desirable to treat both the naphtha and the distillate fractions. Optionally, a portion of the vacuum gas oil fraction could also be treated.
While hydrotreatment (such as fixed bed or trickle bed hydrotreatment) can be effective for saturating such olefins, performing hydrotreatment requires a separate source of hydrogen. At a remote site, excess hydrogen is typically not readily available from other processes.
100171 Instead of performing hydrotreatment, in various aspects of the present disclosure, a catalytic reforming stage can be used to saturate olefins within the naphtha and/or distillate boiling range portions of the partially upgraded bitumen. In addition to forming aromatics, it has been discovered that catalytic reforming can be used to saturate olefins within the naphtha and distillate fractions of a partially upgraded bitumen. Rather than requiring an external source of hydrogen, Date Recue/Date Received 2020-09-03 catalytic reforming provides a method for saturating olefins and/or converting within the naphtha and/or distillate fractions while producing excess hydrogen. Without being bound by any particular theory, it is believed that olefins can be converted to aromatic ring structures under the conditions of a reforming process. Additionally, it is believed that the olefins can be saturated "in-situ" by H2 generated in the reforming environment. This hydrogen is generated as aromatics are formed from naphthenes and/or as olefins are formed from paraffins within the catalytic reforming process.
100181 Using a reforming stage instead of a hydrotreatment stage for olefin reduction can allow for other integration opportunities. For example, the hydrogen generated by reforming can be used to provide hydrogen to the partial upgrading process, when the partial upgrading corresponds to sodium desulfurization, visbreaking in the presence of hydrogen and/or a hydrogen donor solvent, or some type of hydroprocessing. As another example, any light ends (C4_) compounds generated during reforming can be used as fuel gas to provide heat for the partial upgrading process.
100191 Still a further advantage of using reforming instead of hydrotreatment for olefin saturation is that the reformed naphtha and distillate fractions can have an increased content of aromatics. This can increase the solvency of the naphtha and distillate fractions, thus potentially reducing the amount of upgrading that is needed to achieve a desired set of transport properties.
100201 Yet another potential advantage is that the reforming stage may provide a further viscosity reduction for the portions of the partially upgraded effluent that are exposed to the reforming conditions. In some aspects, the kinematic viscosity at 7.5 C for the partially upgraded product can be lower than the kinematic viscosity at 7.5 C for the partial upgrading effluent by 10 cSt or more.
Definitions 100211 In this discussion, the relative severity of visbreaking processes can be compared by referring to a severity index. Severity (or severity index, SI) is a function of reaction time and temperature used during visbreaking. It provides an indication of the severity of the reaction and can be used to compare results of reactions carried out at different conditions. The severity index is defined as:
(1) S/ = t exp[¨ ¨RE (¨T1 ¨ ¨7010)1 100221 In Equation (1), t is the reaction time in seconds, E is the activation energy associated with bitumen thermal cracking, R is the universal gas constant and T is the reaction temperature.
Date Recue/Date Received 2020-09-03 The severity index equals the time required in seconds at 427 C (700 K) to achieve the same degree of reaction (e.g. pitch conversion). For conversion of bitumen, E can generally be set to a value between 50 kcal/mol to 55 kcal/mol.
100231 In this discussion, a hydrogen donor solvent refers to a solvent that can be added to bitumen during processing to allow for higher severity while reducing or minimizing coking. The hydrogen donor solvent can have a higher hydrogen to carbon ratio (i.e., a higher hydrogen content) than the bitumen. For bitumen processing, a recycle fraction from a partially upgraded effluent, such as a recycled naphtha, distillate and/or vacuum gas oil fraction, can be a suitable hydrogen donor solvent. In some aspects, it is noted that addition of a hydrogen donor solvent can potentially provide an additional benefit by acting as a diluent for the feed. This can improve flow properties, such as kinematic viscosity and/or density, which could facilitate cracking.
100241 In this discussion, a fuel gas is defined as a fraction that includes a sufficient amount of Ci ¨ C4 components to be suitable for combustion as a fuel, such as about 5.0 vol% or more of Ci ¨
C4 components, or 10 vol% or more, or 20 vol% or more. Fuel gas can optionally include a variety of other components, such as nitrogen, carbon dioxide, water, and/or other typical components of air; other fuel components such as hydrogen or carbon monoxide; and/or other components that are gases at 25 C and 100 kPa-a.
100251 In this discussion, unless otherwise specified, "conversion" of a feedstock or other input stream is defined as conversion relative to a conversion temperature of 566 C
(1050 F). Once-through conversion refers to the amount of conversion that occurs during a single pass through a reactor / stage / reaction system. Total conversion refers to the net products from the reactor / stage / reaction system, so that any recycle streams are included in the calculation of the total conversion.
It is noted that in all aspects described herein, the amount of conversion at 524 C is lower than the corresponding conversion at 566 C.
100261 In this discussion, a "Cx" hydrocarbon refers to a hydrocarbon compound that includes "x" number of carbons in the compound. A stream containing "Cx ¨ Cy"
hydrocarbons refers to a stream composed of one or more hydrocarbon compounds that includes at least "x" carbons and no more than "y" carbons in the compound. It is noted that a stream comprising G
¨ Cy hydrocarbons may also include other types of hydrocarbons, unless otherwise specified.
- 6 -Date Recue/Date Received 2020-09-03 [0027] In this discussion, "Tx" refers to the temperature at which a weight fraction "x" of a sample can be boiled or distilled. For example, if the temperature at which 40 wt% of a sample has vaporized (i.e., boiled) at atmospheric pressure is 343 C, the sample can be described as having a T40 distillation point of 343 C. In this discussion, boiling points can be determined by a convenient method based on the boiling range of the sample. This can correspond to ASTM
D2887, or for heavier samples ASTM D7169.
[0028] In various aspects of the invention, reference may be made to one or more types of fractions generated during distillation of a petroleum feedstock, intermediate product, and/or product. Such fractions may include naphtha fractions, distillate fuel fractions, and vacuum gas oil fractions. Each of these types of fractions can be defined based on a boiling range, such as a boiling range that includes at least 90 wt% of the fraction, or at least 95 wt% of the fraction. For example, for naphtha fractions, at least 90 wt% of the fraction, or at least 95 wt%, can have a boiling point in the range of 85 F (29 C) to 350 F (177 C). It is noted that 29 C roughly corresponds to the boiling point of isopentane, a C5 hydrocarbon. For a distillate fuel fraction, at least 90 wt% of the fraction, or at least 95 wt%, can have a boiling point in the range of 350 F (177 C) to 650 F (343 C). For a vacuum gas oil fraction, at least 90 wt% of the fraction, or at least 95 wt%, can have a boiling point in the range of 650 F (343 C) to 1050 F (566 C). Fractions boiling below the naphtha range can sometimes be referred to as light ends. Fractions boiling above the vacuum gas oil range can be referred to as vacuum resid fractions or pitch fractions.
[0029] In this discussion, the boiling range of components in a feed, intermediate product, and/or final product may alternatively be described based on describing a weight percentage of components that boil within a defined range. The defined range can correspond to a range with an lower boiling temperature bound, such as components that boil at less than 177 C (referred to as 177 C-); a range with a upper boiling temperature bound, such as components that boil at greater than 566 C (referred to as 566 C+); or within or outside of a range with both a lower bound and an upper bound, such as 343 C ¨ 566 C.
[0030] Preparing heavy hydrocarbon feeds for pipeline transport often involves achieving target values for a plurality of separate properties. First, the viscosity of the processed heavy hydrocarbon feed needs to be suitable or roughly suitable for pipeline transport. This can correspond to, for example, having a kinematic viscosity at 7.5 C of 360 cSt or less, or 350 cSt or less, such as down
D2887, or for heavier samples ASTM D7169.
[0028] In various aspects of the invention, reference may be made to one or more types of fractions generated during distillation of a petroleum feedstock, intermediate product, and/or product. Such fractions may include naphtha fractions, distillate fuel fractions, and vacuum gas oil fractions. Each of these types of fractions can be defined based on a boiling range, such as a boiling range that includes at least 90 wt% of the fraction, or at least 95 wt% of the fraction. For example, for naphtha fractions, at least 90 wt% of the fraction, or at least 95 wt%, can have a boiling point in the range of 85 F (29 C) to 350 F (177 C). It is noted that 29 C roughly corresponds to the boiling point of isopentane, a C5 hydrocarbon. For a distillate fuel fraction, at least 90 wt% of the fraction, or at least 95 wt%, can have a boiling point in the range of 350 F (177 C) to 650 F (343 C). For a vacuum gas oil fraction, at least 90 wt% of the fraction, or at least 95 wt%, can have a boiling point in the range of 650 F (343 C) to 1050 F (566 C). Fractions boiling below the naphtha range can sometimes be referred to as light ends. Fractions boiling above the vacuum gas oil range can be referred to as vacuum resid fractions or pitch fractions.
[0029] In this discussion, the boiling range of components in a feed, intermediate product, and/or final product may alternatively be described based on describing a weight percentage of components that boil within a defined range. The defined range can correspond to a range with an lower boiling temperature bound, such as components that boil at less than 177 C (referred to as 177 C-); a range with a upper boiling temperature bound, such as components that boil at greater than 566 C (referred to as 566 C+); or within or outside of a range with both a lower bound and an upper bound, such as 343 C ¨ 566 C.
[0030] Preparing heavy hydrocarbon feeds for pipeline transport often involves achieving target values for a plurality of separate properties. First, the viscosity of the processed heavy hydrocarbon feed needs to be suitable or roughly suitable for pipeline transport. This can correspond to, for example, having a kinematic viscosity at 7.5 C of 360 cSt or less, or 350 cSt or less, such as down
- 7 -Date Recue/Date Received 2020-09-03 to 250 cSt or possibly still lower. Second, the density of the processed heavy hydrocarbon feed needs to be suitable or roughly suitable for pipeline transport. This can correspond to, for example, having an API Gravity of 18 or more, or 190 or more. Third, an olefin content of the processed heavy hydrocarbon feed also needs to be sufficiently low, such as having an olefin content of 1.0 wt% or less. In some aspects, a relaxed set of properties may be sufficient to satisfy transport standards, so that having an API gravity of 14 or more and/or a kinematic viscosity at 7.5 C of 500 cSt or less is sufficient.
100311 In this discussion, a stage is defined as a portion of a reaction system. A stage can include one or more reactors and/or other process elements. For example, a partial upgrading stage can include a single reactor or a plurality of reactors. If separations may be conventionally performed between reactors within a stage, such separations may optionally be present, unless otherwise specified. More generally, if other flow management features are conventionally present within a stage, such features may also optionally be present, unless otherwise specified. For example, a reforming stage can often include recycle of a portion of the overhead gas from the reforming effluent in order to introduce hydrogen into the reforming reaction environment.
Reforming Stage and Integration for Partial Upgrading of Bitumen 100321 In various aspects, a catalytic reforming stage can be used to reduce or minimize the olefin content in a portion of a partially upgraded bitumen feed (or more generally, a partially upgraded heavy hydrocarbon feed). Depending on the nature of the partial upgrading and the nature of the bitumen, several options are available for selecting the portion of the partially upgraded bitumen for reforming. The portion of the partially upgraded bitumen used as the input for reforming can correspond to a naphtha boiling range portion, a distillate boiling range portion, or a combination thereof. Optionally, the input can include a portion of vacuum gas oil boiling range material. Generally, this can correspond to having an input flow to reforming with a T5 distillation point of 29 C or more and a T95 distillation point of 400 C or less. If vacuum gas oil boiling range components are not desired, the T95 distillation point can be lower, such as 370 C or less, or 343 C
or less. In aspects where only a naphtha boiling range portion is reformed, the T5 distillation point can be 29 C or more and the T95 distillation point can be 204 C or less (if heavy naphtha is included), or 177 C or less. In aspects where only a distillate boiling range portion is reformed, the
100311 In this discussion, a stage is defined as a portion of a reaction system. A stage can include one or more reactors and/or other process elements. For example, a partial upgrading stage can include a single reactor or a plurality of reactors. If separations may be conventionally performed between reactors within a stage, such separations may optionally be present, unless otherwise specified. More generally, if other flow management features are conventionally present within a stage, such features may also optionally be present, unless otherwise specified. For example, a reforming stage can often include recycle of a portion of the overhead gas from the reforming effluent in order to introduce hydrogen into the reforming reaction environment.
Reforming Stage and Integration for Partial Upgrading of Bitumen 100321 In various aspects, a catalytic reforming stage can be used to reduce or minimize the olefin content in a portion of a partially upgraded bitumen feed (or more generally, a partially upgraded heavy hydrocarbon feed). Depending on the nature of the partial upgrading and the nature of the bitumen, several options are available for selecting the portion of the partially upgraded bitumen for reforming. The portion of the partially upgraded bitumen used as the input for reforming can correspond to a naphtha boiling range portion, a distillate boiling range portion, or a combination thereof. Optionally, the input can include a portion of vacuum gas oil boiling range material. Generally, this can correspond to having an input flow to reforming with a T5 distillation point of 29 C or more and a T95 distillation point of 400 C or less. If vacuum gas oil boiling range components are not desired, the T95 distillation point can be lower, such as 370 C or less, or 343 C
or less. In aspects where only a naphtha boiling range portion is reformed, the T5 distillation point can be 29 C or more and the T95 distillation point can be 204 C or less (if heavy naphtha is included), or 177 C or less. In aspects where only a distillate boiling range portion is reformed, the
- 8 -Date Recue/Date Received 2020-09-03 T5 distillation point can be 177 C or more and the T95 distillation point can be 400 C or less, or 370 C or less, or 343 C or less.
100331 In aspects where the input flow to reforming includes a distillate boiling range portion, the input flow can correspond to an input flow having an unusually high boiling range for a reforming process, due to the presence of components that boil above 260 C, or the presence of components that boil above the kerosene boiling range (i.e., above 300 C). For example, 10 wt%
or more of the input flow can correspond to components with a boiling point above 260 C, or 20 wt% or more, or 30 wt% or more. In some aspects, 10 wt% or more of the input flow can correspond to components with a boiling point greater than 300 C, or 20 wt% or more, or 30 wt% or more. It is noted that this could be similarly described as an input flow with a T90 distillation point greater than 260 C (or 300 C), or a T80 distillation point greater than 260 C (or 300 C), or a T70 distillation point greater than 260 C (or 300 C).
100341 Due to the high sulfur content of bitumen feeds, the naphtha and distillate fractions from partial upgrading can also have relatively high sulfur contents. The amount of sulfur can vary depending on the type of partial upgrading. Depending on the aspect the sulfur content of the naphtha fractions can range from 10 wppm to 1500 wppm, with values of 100 wppm or more being more typical of most partial upgrading methods. Partially upgraded distillate fractions can include still higher sulfur contents.
100351 In reforming, a multi-functional catalyst is employed which contains a metal hydrogenation-dehydrogenation (hydrogen transfer) component, or components, substantially atomically dispersed upon the surface of a porous, inorganic oxide support, such as alumina. For conventional reforming of low sulfur naphtha fractions, noble metal catalysts (such as platinum catalysts) are currently employed. However, platinum metal catalysts can foul rapidly under exposure to high sulfur content feeds resulting in a significant loss of reforming activity. In an embodiment of the present invention, the reformer feed from the process configurations described herein can have a sulfur content of 100 wppm or more, and a non-noble active metal catalyst, such as a catalyst comprising nickel as the active metal, may be preferably utilized in the reforming stage.
100361 A reforming process can be defined as the total effect of the molecular changes, or hydrocarbon reactions. The naphthene portion of the naphtha stream is dehydrogenated to the corresponding aromatic compounds, the normal paraffins are isomerized to branched chain
100331 In aspects where the input flow to reforming includes a distillate boiling range portion, the input flow can correspond to an input flow having an unusually high boiling range for a reforming process, due to the presence of components that boil above 260 C, or the presence of components that boil above the kerosene boiling range (i.e., above 300 C). For example, 10 wt%
or more of the input flow can correspond to components with a boiling point above 260 C, or 20 wt% or more, or 30 wt% or more. In some aspects, 10 wt% or more of the input flow can correspond to components with a boiling point greater than 300 C, or 20 wt% or more, or 30 wt% or more. It is noted that this could be similarly described as an input flow with a T90 distillation point greater than 260 C (or 300 C), or a T80 distillation point greater than 260 C (or 300 C), or a T70 distillation point greater than 260 C (or 300 C).
100341 Due to the high sulfur content of bitumen feeds, the naphtha and distillate fractions from partial upgrading can also have relatively high sulfur contents. The amount of sulfur can vary depending on the type of partial upgrading. Depending on the aspect the sulfur content of the naphtha fractions can range from 10 wppm to 1500 wppm, with values of 100 wppm or more being more typical of most partial upgrading methods. Partially upgraded distillate fractions can include still higher sulfur contents.
100351 In reforming, a multi-functional catalyst is employed which contains a metal hydrogenation-dehydrogenation (hydrogen transfer) component, or components, substantially atomically dispersed upon the surface of a porous, inorganic oxide support, such as alumina. For conventional reforming of low sulfur naphtha fractions, noble metal catalysts (such as platinum catalysts) are currently employed. However, platinum metal catalysts can foul rapidly under exposure to high sulfur content feeds resulting in a significant loss of reforming activity. In an embodiment of the present invention, the reformer feed from the process configurations described herein can have a sulfur content of 100 wppm or more, and a non-noble active metal catalyst, such as a catalyst comprising nickel as the active metal, may be preferably utilized in the reforming stage.
100361 A reforming process can be defined as the total effect of the molecular changes, or hydrocarbon reactions. The naphthene portion of the naphtha stream is dehydrogenated to the corresponding aromatic compounds, the normal paraffins are isomerized to branched chain
- 9 -Date Recue/Date Received 2020-09-03 paraffins, and various aromatics compounds are isomerized to other aromatics.
Additionally, based on the presence of both hydrogen and a catalyst with hydrogenation /
dehydrogenation activity, olefins can be saturated. The high boiling components in the naphtha stream are also hydrocracked to lower boiling components. Specifically, these molecular changes are produced by dehydrogenation of cyclohexanes and dehydroisomerization of alkylcyclopentanes to yield aromatics; dehydrocyclization of paraffins and olefins to yield aromatics;
saturation of olefins;
isomerization of n-paraffins; isomerization of alkylcycloparaffins to yield cyclohexanes;
isomerization of substituted aromatics; and cracking reactions which produce gas.
100371 In a reforming process, one or a series of reactors, providing a series of reaction zones, are employed. A reforming reactor can generally include a fixed bed, or beds, of catalyst, which receive feed. Any convenient reactor configuration can be used, such as downflow or radial flow.
Optionally, each reactor is provided with a preheater, or interstage heater, because the net effect of the reactions which take place is typically endothermic. A naphtha and/or distillate feed, with hydrogen, and/or hydrogen-containing recycle gas, is passed through the preheat furnace then to the reactor, and then in sequence through subsequent interstage heaters and reactors of the series. The product from the last reactor is separated into a liquid fraction and a vaporous fraction, the former usually being recovered as a C5+ liquid product. The latter is rich in hydrogen and usually contains small amounts of normally gaseous hydrocarbons. A portion of the hydrogen-rich overhead can be recycled to the process to minimize coke production.
100381 The input flow to catalytic reforming can contain 20 vol% to 80 vol%
paraffins, 20 vol%
to 80 vol% naphthenes, and 5 vol% to 20 vol% aromatics. The input flow is brought into contact with a catalyst system, such as the catalysts described above, in the presence of hydrogen. The reactions typically take place in the vapor phase at a temperature varying from about 343 C (650 F) to 538 C (1000 F), or 400 C to 538 C, or 400 C to 500 C. Reaction zone pressures may vary from 100 to 5000 kPa-g, preferably 500 to 2500 kPa-g. It is noted that due to the relatively high sulfur content of partially upgraded bitumen, as well as the potential presence of other contaminants, some increase in reaction severity may be needed to compensate for the reaction environment. On the other hand, the reforming process is being performed primarily for olefin removal and H2 production. This can require lower severity conditions than a reforming reaction for improving the octane of naphtha.
Additionally, based on the presence of both hydrogen and a catalyst with hydrogenation /
dehydrogenation activity, olefins can be saturated. The high boiling components in the naphtha stream are also hydrocracked to lower boiling components. Specifically, these molecular changes are produced by dehydrogenation of cyclohexanes and dehydroisomerization of alkylcyclopentanes to yield aromatics; dehydrocyclization of paraffins and olefins to yield aromatics;
saturation of olefins;
isomerization of n-paraffins; isomerization of alkylcycloparaffins to yield cyclohexanes;
isomerization of substituted aromatics; and cracking reactions which produce gas.
100371 In a reforming process, one or a series of reactors, providing a series of reaction zones, are employed. A reforming reactor can generally include a fixed bed, or beds, of catalyst, which receive feed. Any convenient reactor configuration can be used, such as downflow or radial flow.
Optionally, each reactor is provided with a preheater, or interstage heater, because the net effect of the reactions which take place is typically endothermic. A naphtha and/or distillate feed, with hydrogen, and/or hydrogen-containing recycle gas, is passed through the preheat furnace then to the reactor, and then in sequence through subsequent interstage heaters and reactors of the series. The product from the last reactor is separated into a liquid fraction and a vaporous fraction, the former usually being recovered as a C5+ liquid product. The latter is rich in hydrogen and usually contains small amounts of normally gaseous hydrocarbons. A portion of the hydrogen-rich overhead can be recycled to the process to minimize coke production.
100381 The input flow to catalytic reforming can contain 20 vol% to 80 vol%
paraffins, 20 vol%
to 80 vol% naphthenes, and 5 vol% to 20 vol% aromatics. The input flow is brought into contact with a catalyst system, such as the catalysts described above, in the presence of hydrogen. The reactions typically take place in the vapor phase at a temperature varying from about 343 C (650 F) to 538 C (1000 F), or 400 C to 538 C, or 400 C to 500 C. Reaction zone pressures may vary from 100 to 5000 kPa-g, preferably 500 to 2500 kPa-g. It is noted that due to the relatively high sulfur content of partially upgraded bitumen, as well as the potential presence of other contaminants, some increase in reaction severity may be needed to compensate for the reaction environment. On the other hand, the reforming process is being performed primarily for olefin removal and H2 production. This can require lower severity conditions than a reforming reaction for improving the octane of naphtha.
- 10 -Date Recue/Date Received 2020-09-03 100391 The input flow is generally passed over the catalyst at a weight hourly space velocity of 0.1 to 20 hr-1, preferably from about 1 to 10 w/hr/w. The hydrogen to hydrocarbon mole ratio within the reaction zone is maintained between about 0.5 and 20, preferably between about 1 and 10.
100401 The reformed effluent can have various properties that are modified relative to the input flow to the reforming stage. In some aspects, the olefin content of the reformed effluent can be 1.0 wt% or less, or 0.8 wt% or less, or 0.5 wt% or less, or 0.2 wt% or less, such as down to 0.05 wt%
or possibly still lower. While aromatics will also be formed, any convenient amount of aromatics can be generated during reforming, so long as the desired olefin reduction occurs. This can be in contrast to some conventional reforming conditions, where the goal is to increase the aromatic content of the input flow to reforming. Depending on the aspect, the aromatics content of the reformed effluent can be greater than the aromatics content of the input flow to the reforming stage by 1.0 wt% to 20 wt%, or 1.0 wt% to 10 wt%, or 5.0 wt% to 20 wt%.
100411 Figure 1 shows an example of how a reforming stage can be integrated into a system for partial upgrading of bitumen (or another type of heavy hydrocarbon feed). In the example shown in Figure 1, a heavy hydrocarbon feed such as bitumen 105 is passed into a partial upgrading reaction system 110. Any convenient type of partial upgrading stage can be used. Examples of suitable partial upgrading include, but are not limited to, visbreaking (optionally in the presence of a hydrogen donor solvent), sodium desulfurization, slurry hydrocracking, other types of thermal cracking, and/or various types of hydroprocessing. In the example shown in Figure 1, the partial upgrading stage is heated 179 using a fired heater 170. The fuel for fired heater 170 can optionally correspond to fuel gas stream 162.
100421 The partial upgrader 110 can produce a partially upgraded effluent 115. In the example shown in Figure 1, the partially upgraded effluent 115 is then separated 120 into a lower boiling fraction 125 including the naphtha and distillate boiling range portions from the partially upgraded effluent, and a higher boiling fraction 145 that includes the vacuum gas oil and resid portions. It is understood that in other aspects, any other convenient choice could be made for separating 120 the partially upgraded effluent. For example, some or all of the distillate could be included in the higher boiling portion 145, or some of the vacuum gas oil could be included in the lower boiling portion 125. In still other aspects, separate naphtha and distillate fractions could be formed (not shown), to allow for exposure of the naphtha fraction and distillate fraction to separate reforming conditions.
100401 The reformed effluent can have various properties that are modified relative to the input flow to the reforming stage. In some aspects, the olefin content of the reformed effluent can be 1.0 wt% or less, or 0.8 wt% or less, or 0.5 wt% or less, or 0.2 wt% or less, such as down to 0.05 wt%
or possibly still lower. While aromatics will also be formed, any convenient amount of aromatics can be generated during reforming, so long as the desired olefin reduction occurs. This can be in contrast to some conventional reforming conditions, where the goal is to increase the aromatic content of the input flow to reforming. Depending on the aspect, the aromatics content of the reformed effluent can be greater than the aromatics content of the input flow to the reforming stage by 1.0 wt% to 20 wt%, or 1.0 wt% to 10 wt%, or 5.0 wt% to 20 wt%.
100411 Figure 1 shows an example of how a reforming stage can be integrated into a system for partial upgrading of bitumen (or another type of heavy hydrocarbon feed). In the example shown in Figure 1, a heavy hydrocarbon feed such as bitumen 105 is passed into a partial upgrading reaction system 110. Any convenient type of partial upgrading stage can be used. Examples of suitable partial upgrading include, but are not limited to, visbreaking (optionally in the presence of a hydrogen donor solvent), sodium desulfurization, slurry hydrocracking, other types of thermal cracking, and/or various types of hydroprocessing. In the example shown in Figure 1, the partial upgrading stage is heated 179 using a fired heater 170. The fuel for fired heater 170 can optionally correspond to fuel gas stream 162.
100421 The partial upgrader 110 can produce a partially upgraded effluent 115. In the example shown in Figure 1, the partially upgraded effluent 115 is then separated 120 into a lower boiling fraction 125 including the naphtha and distillate boiling range portions from the partially upgraded effluent, and a higher boiling fraction 145 that includes the vacuum gas oil and resid portions. It is understood that in other aspects, any other convenient choice could be made for separating 120 the partially upgraded effluent. For example, some or all of the distillate could be included in the higher boiling portion 145, or some of the vacuum gas oil could be included in the lower boiling portion 125. In still other aspects, separate naphtha and distillate fractions could be formed (not shown), to allow for exposure of the naphtha fraction and distillate fraction to separate reforming conditions.
-11 -Date Recue/Date Received 2020-09-03 Due to the nature of the reforming conditions, inclusion of vacuum resid and/or heavier portions of the vacuum gas oil could result in excessive coke formation and/or fouling under catalytic reforming conditions.
100431 In aspects where only heavier portions of the initial bitumen feed are passed into the partial upgrading stage, a portion of the feed to reforming stage 130 can correspond to virgin naphtha and/or virgin distillate that have been separated from the bitumen prior to the partial upgrading stage.
While virgin naphtha and virgin distillate typically include only minimal olefin content, such virgin naphtha and/or distillate fractions could allow for further aromatics production which are beneficial to the flow characteristics of the final pipeline product.
100441 The lower boiling portion 125 can then be passed into reforming stage 130. The reforming stage produces a reformed effluent 135 and a reformer overhead stream 132. The reformed effluent 135 can then be recombined with higher boiling fraction 145 in blending stage 150 to form a partially upgraded product 155 with an olefin content that is suitable for transport, such as an olefin content of 1.0 wt% or less that is suitable for pipeline transport. It is noted that any portion of initial feed 105 that bypasses (not shown) the partial upgrading stage 110 can also be incorporated into the partially upgraded product 155. Optionally, a diluent can also be added to the partially upgraded product 155 in blending stage 150 to assist with satisfying other transport specifications.
100451 In the example shown in Figure 1, the reformer overhead stream 132 can be passed into a gas separation unit 160. This can allow for separation of a hydrogen-enriched stream 161 from a fuel gas stream 162. The hydrogen-enriched stream can correspond to a stream containing 30 vol%
or more of H2, or 50 vol% or more, such as up to 90 vol% or possibly still higher. The balance of the hydrogen-enriched stream can be other components from the reforming reaction environment, such as nitrogen, water, and/or Ci ¨ C4 hydrocarbons. The fuel gas 162 can have a lower hydrogen content than the hydrogen-enriched stream 161. In aspects where partial upgrading stage 110 benefits from having hydrogen in the reaction environment, hydrogen-enriched stream 161 can be used to provide at least part of such hydrogen. In aspects where hydrogen is not needed for operation of partial upgrading stage 110, the hydrogen can be used for other purposes, or can be used as a second fuel stream for heater 170. Optionally, the hydrogen-enriched stream 161 can form part of the recycled hydrogen (not shown) that is returned to reforming stage 130.
100431 In aspects where only heavier portions of the initial bitumen feed are passed into the partial upgrading stage, a portion of the feed to reforming stage 130 can correspond to virgin naphtha and/or virgin distillate that have been separated from the bitumen prior to the partial upgrading stage.
While virgin naphtha and virgin distillate typically include only minimal olefin content, such virgin naphtha and/or distillate fractions could allow for further aromatics production which are beneficial to the flow characteristics of the final pipeline product.
100441 The lower boiling portion 125 can then be passed into reforming stage 130. The reforming stage produces a reformed effluent 135 and a reformer overhead stream 132. The reformed effluent 135 can then be recombined with higher boiling fraction 145 in blending stage 150 to form a partially upgraded product 155 with an olefin content that is suitable for transport, such as an olefin content of 1.0 wt% or less that is suitable for pipeline transport. It is noted that any portion of initial feed 105 that bypasses (not shown) the partial upgrading stage 110 can also be incorporated into the partially upgraded product 155. Optionally, a diluent can also be added to the partially upgraded product 155 in blending stage 150 to assist with satisfying other transport specifications.
100451 In the example shown in Figure 1, the reformer overhead stream 132 can be passed into a gas separation unit 160. This can allow for separation of a hydrogen-enriched stream 161 from a fuel gas stream 162. The hydrogen-enriched stream can correspond to a stream containing 30 vol%
or more of H2, or 50 vol% or more, such as up to 90 vol% or possibly still higher. The balance of the hydrogen-enriched stream can be other components from the reforming reaction environment, such as nitrogen, water, and/or Ci ¨ C4 hydrocarbons. The fuel gas 162 can have a lower hydrogen content than the hydrogen-enriched stream 161. In aspects where partial upgrading stage 110 benefits from having hydrogen in the reaction environment, hydrogen-enriched stream 161 can be used to provide at least part of such hydrogen. In aspects where hydrogen is not needed for operation of partial upgrading stage 110, the hydrogen can be used for other purposes, or can be used as a second fuel stream for heater 170. Optionally, the hydrogen-enriched stream 161 can form part of the recycled hydrogen (not shown) that is returned to reforming stage 130.
- 12 -Date Recue/Date Received 2020-09-03 Bitumen and Other Heavy Hydrocarbon Feedstocks [0046] In various aspects, the initial feed to the partial upgrading stage can correspond to a bitumen and/or another type of heavy hydrocarbon feed. A bitumen feed can correspond to a bitumen formed from oil sands (or another heavy hydrocarbon feed) by any convenient method.
Such methods include, but are not limited to, a paraffinic froth treatment process, a naphtha froth treatment, a cyclic steam stimulation (CSS) process, a liquid addition to steam to enhance recovery (LASER) process, a steam-assisted gravity drainage process (SAGD), solvent-assisted steam-assisted gravity drainage (SA-SAGD) process, a heated vapor extraction (VAPEX) process, a cyclic solvent process (CSP), or a combination thereof. Other examples of heavy hydrocarbon feeds include, but are not limited to, heavy crude oils, and heavy oils derived from coal, and blends of such feeds. In some aspects, heavy hydrocarbon feeds can also include at least a portion corresponding to a heavy refinery fraction, such as distillation residues, heavy oils coming from catalytic treatment (such as heavy cycle slurry oils or main column bottoms from fluid catalytic cracking), and/or thermal tars (such as oils from visbreaking, steam cracking, or similar thermal or non-catalytic processes). Heavy hydrocarbon feeds can be liquid or semi-solid.
Such heavy hydrocarbon feeds can include a substantial portion of the feed that boils at 650 F (343 C) or higher.
For example, the portion of a heavy hydrocarbon feed that boils at less than 650 F (343 C) can correspond to 5 wt% to 40 wt% of the feed, or 10 wt% to 30 wt% of the feed, or 5 wt% to 20 wt%
of the feed. In such aspects, the heavy hydrocarbon feed can have a T40 distillation point of 343 C
or higher, or a T30 distillation point of 343 C or higher, or a T20 distillation point of 343 C or higher. Additionally or alternately, a substantial portion of a heavy hydrocarbon feed can also correspond to compounds with a boiling point of 566 C or higher. For example, a heavy hydrocarbon feed can have a T80 distillation point of 566 C or higher, or a T70 distillation point of 566 C or higher, or a T60 distillation point of 566 C or higher, or a T50 distillation point of 566 C
or higher.
[0047] Density, or weight per volume, of the heavy hydrocarbon can be determined according to ASTM D287 - 92 (2006) Standard Test Method for API Gravity of Crude Petroleum and Petroleum Products (Hydrometer Method), and is provided in terms of API
gravity. In general, the higher the API gravity, the less dense the oil. API gravity can be 16 or less, or 12 or less, or 8 or less. Additionally or alternately, the density at 15 C of the bitumen (or other heavy hydrocarbon
Such methods include, but are not limited to, a paraffinic froth treatment process, a naphtha froth treatment, a cyclic steam stimulation (CSS) process, a liquid addition to steam to enhance recovery (LASER) process, a steam-assisted gravity drainage process (SAGD), solvent-assisted steam-assisted gravity drainage (SA-SAGD) process, a heated vapor extraction (VAPEX) process, a cyclic solvent process (CSP), or a combination thereof. Other examples of heavy hydrocarbon feeds include, but are not limited to, heavy crude oils, and heavy oils derived from coal, and blends of such feeds. In some aspects, heavy hydrocarbon feeds can also include at least a portion corresponding to a heavy refinery fraction, such as distillation residues, heavy oils coming from catalytic treatment (such as heavy cycle slurry oils or main column bottoms from fluid catalytic cracking), and/or thermal tars (such as oils from visbreaking, steam cracking, or similar thermal or non-catalytic processes). Heavy hydrocarbon feeds can be liquid or semi-solid.
Such heavy hydrocarbon feeds can include a substantial portion of the feed that boils at 650 F (343 C) or higher.
For example, the portion of a heavy hydrocarbon feed that boils at less than 650 F (343 C) can correspond to 5 wt% to 40 wt% of the feed, or 10 wt% to 30 wt% of the feed, or 5 wt% to 20 wt%
of the feed. In such aspects, the heavy hydrocarbon feed can have a T40 distillation point of 343 C
or higher, or a T30 distillation point of 343 C or higher, or a T20 distillation point of 343 C or higher. Additionally or alternately, a substantial portion of a heavy hydrocarbon feed can also correspond to compounds with a boiling point of 566 C or higher. For example, a heavy hydrocarbon feed can have a T80 distillation point of 566 C or higher, or a T70 distillation point of 566 C or higher, or a T60 distillation point of 566 C or higher, or a T50 distillation point of 566 C
or higher.
[0047] Density, or weight per volume, of the heavy hydrocarbon can be determined according to ASTM D287 - 92 (2006) Standard Test Method for API Gravity of Crude Petroleum and Petroleum Products (Hydrometer Method), and is provided in terms of API
gravity. In general, the higher the API gravity, the less dense the oil. API gravity can be 16 or less, or 12 or less, or 8 or less. Additionally or alternately, the density at 15 C of the bitumen (or other heavy hydrocarbon
- 13 -Date Recue/Date Received 2020-09-03 feed) can be 0.95 g/cm3 to 1.2 g/cm3, or possibly still higher. Further additionally or alternately, the kinematic viscosity of the feed at 7.5 C can be 500 cSt or greater. This can be determined according to the test method specified in ASTM D2170, although the temperature differs from the test specification.
100481 Heavy hydrocarbon feeds can be high in metals. For example, the heavy hydrocarbon feed can be high in total nickel, vanadium and iron contents. In one embodiment, the heavy oil will contain at least 0.00005 grams of Ni/V/Fe (50 ppm) or at least 0.0002 grams of Ni/V/Fe (200 ppm) per gram of heavy oil, on a total elemental basis of nickel, vanadium and iron. In other aspects, the heavy oil can contain at least about 500 wppm of nickel, vanadium, and iron, such as at least about 1000 wppm.
100491 Contaminants such as nitrogen and sulfur are typically found in heavy hydrocarbon feeds, often in organically-bound form. Nitrogen content can range from about 0.1 wt% to about 3.0 wt% elemental nitrogen, or 1.0 wt% to 3.0 wt%, or 0.1 wt% to 1.0 wt%, based on total weight of the heavy hydrocarbon feed. Generally, the sulfur content can range from 0.1 wt% to 10 wt%
elemental sulfur, or 1.0 wt% to 10 wt%, or 0.1 wt% to 5.0 wt%, or 1.0 wt% to 7.0 wt%, based on total weight of the heavy hydrocarbon feed. Sulfur will usually be present as organically bound sulfur.
100501 Heavy hydrocarbon feeds can be high in n-pentane asphaltenes and/or n-heptane asphaltenes. In some aspects, the heavy hydrocarbon feed can contain 5.0 wt%
or more of n-pentane asphaltenes, or 10 wt% or more, or 15 wt% or more, such as up to 30 wt% or possibly still higher.
Additionally or alternately, the heavy hydrocarbon feed can contain 3.0 wt% or more of n-heptane asphaltenes, or 5.0 wt% or more, or 10 wt% or more, such as up to 25 wt% or possibly still higher.
In other aspects, the heavy hydrocarbon feed can correspond to a feed that is at least partially derived from performing a froth treatment on oil sands, such as a paraffinic froth treatment. In such aspects, the amount of n-heptane asphaltenes can be 15 wt% or less, or 10 wt% or less, or 5.0 wt% or less, such as down to 1.0 wt% or possibly still lower. In yet other aspects, a modified froth treatment can be used that allows an increased amount of asphaltenes to be retained in the bitumen after froth treatment. In such aspects, the amount of n-heptane asphaltenes can be 5.0 wt%
to 20 wt%, or 5.0 wt% to 15 wt%, or 10 wt% to 20 wt%
100481 Heavy hydrocarbon feeds can be high in metals. For example, the heavy hydrocarbon feed can be high in total nickel, vanadium and iron contents. In one embodiment, the heavy oil will contain at least 0.00005 grams of Ni/V/Fe (50 ppm) or at least 0.0002 grams of Ni/V/Fe (200 ppm) per gram of heavy oil, on a total elemental basis of nickel, vanadium and iron. In other aspects, the heavy oil can contain at least about 500 wppm of nickel, vanadium, and iron, such as at least about 1000 wppm.
100491 Contaminants such as nitrogen and sulfur are typically found in heavy hydrocarbon feeds, often in organically-bound form. Nitrogen content can range from about 0.1 wt% to about 3.0 wt% elemental nitrogen, or 1.0 wt% to 3.0 wt%, or 0.1 wt% to 1.0 wt%, based on total weight of the heavy hydrocarbon feed. Generally, the sulfur content can range from 0.1 wt% to 10 wt%
elemental sulfur, or 1.0 wt% to 10 wt%, or 0.1 wt% to 5.0 wt%, or 1.0 wt% to 7.0 wt%, based on total weight of the heavy hydrocarbon feed. Sulfur will usually be present as organically bound sulfur.
100501 Heavy hydrocarbon feeds can be high in n-pentane asphaltenes and/or n-heptane asphaltenes. In some aspects, the heavy hydrocarbon feed can contain 5.0 wt%
or more of n-pentane asphaltenes, or 10 wt% or more, or 15 wt% or more, such as up to 30 wt% or possibly still higher.
Additionally or alternately, the heavy hydrocarbon feed can contain 3.0 wt% or more of n-heptane asphaltenes, or 5.0 wt% or more, or 10 wt% or more, such as up to 25 wt% or possibly still higher.
In other aspects, the heavy hydrocarbon feed can correspond to a feed that is at least partially derived from performing a froth treatment on oil sands, such as a paraffinic froth treatment. In such aspects, the amount of n-heptane asphaltenes can be 15 wt% or less, or 10 wt% or less, or 5.0 wt% or less, such as down to 1.0 wt% or possibly still lower. In yet other aspects, a modified froth treatment can be used that allows an increased amount of asphaltenes to be retained in the bitumen after froth treatment. In such aspects, the amount of n-heptane asphaltenes can be 5.0 wt%
to 20 wt%, or 5.0 wt% to 15 wt%, or 10 wt% to 20 wt%
- 14 -Date Recue/Date Received 2020-09-03 100511 Still another method for characterizing a heavy hydrocarbon feed is based on the Conradson carbon residue of the feedstock, or alternatively the micro carbon residue content. The Conradson carbon residue / micro carbon residue content of the feedstock can be 5.0 wt% to 50 wt%, or 5.0 wt% to 30 wt%, or 10 wt% to 40 wt%, or 20 wt% to 50 wt%.
100521 In some optional aspects, rather than performing partial upgrading on the bitumen and/or heavy hydrocarbon feed, a fractionation can be performed so that only a portion of the feed is exposed to the partial upgrading conditions. In aspects where fractionation is performed prior to partial upgrading, the fractionation stage can include components for performing an atmospheric distillation, a vacuum distillation, one or more flash separations, or a combination thereof.
Optionally, one or more solvent deasphalting units can also be used. As an example, a separation can be performed on a heavy hydrocarbon feed to form a lower boiling (lighter) fraction and a higher boiling (heavier) fraction. The heavier fraction can have a T50 distillation point of 400 C or more, or 500 C or more. Additionally, the T50 distillation point of the lighter fraction can be lower than the T50 distillation point of the heavier fraction. The lighter fraction can have a T95 distillation point of 500 C or less, or 400 C or less. Additionally, the T95 distillation point of the heavier fraction can be higher than the T95 distillation point of the lighter fraction.
Example of Partial Upgrading Conditions - Visbreaking 100531 In various aspects, the partial upgrading process can correspond to visbreaking (including visbreaking in the presence of a hydrogen donor solvent), hydroprocessing (such as slurry hydrocracking), coking (such as fluidized coking), or desulfurization (such as sodium desulfurization). In order to illustrate the concepts described herein, additional details are provided for using visbreaking as the method of partial upgrading.
100541 Visbreaking is a thermal upgrading process where a feed is exposed to thermal cracking temperatures, but for a period of time where coking of the feed is reduced or minimized. Since the tendency to form coke can vary with the nature of a feed, the desired severity of a visbreaking process can vary based on the feed. In some aspects, the severity of visbreaking that can be performed without resulting in coking can be increased by adding a donor solvent to the visbreaking environment.
[0055] In most hydrocarbon processes, there is a tradeoff between reaction temperature and residence time of reactants. Because visbreaking is a well-known and widely practiced process,
100521 In some optional aspects, rather than performing partial upgrading on the bitumen and/or heavy hydrocarbon feed, a fractionation can be performed so that only a portion of the feed is exposed to the partial upgrading conditions. In aspects where fractionation is performed prior to partial upgrading, the fractionation stage can include components for performing an atmospheric distillation, a vacuum distillation, one or more flash separations, or a combination thereof.
Optionally, one or more solvent deasphalting units can also be used. As an example, a separation can be performed on a heavy hydrocarbon feed to form a lower boiling (lighter) fraction and a higher boiling (heavier) fraction. The heavier fraction can have a T50 distillation point of 400 C or more, or 500 C or more. Additionally, the T50 distillation point of the lighter fraction can be lower than the T50 distillation point of the heavier fraction. The lighter fraction can have a T95 distillation point of 500 C or less, or 400 C or less. Additionally, the T95 distillation point of the heavier fraction can be higher than the T95 distillation point of the lighter fraction.
Example of Partial Upgrading Conditions - Visbreaking 100531 In various aspects, the partial upgrading process can correspond to visbreaking (including visbreaking in the presence of a hydrogen donor solvent), hydroprocessing (such as slurry hydrocracking), coking (such as fluidized coking), or desulfurization (such as sodium desulfurization). In order to illustrate the concepts described herein, additional details are provided for using visbreaking as the method of partial upgrading.
100541 Visbreaking is a thermal upgrading process where a feed is exposed to thermal cracking temperatures, but for a period of time where coking of the feed is reduced or minimized. Since the tendency to form coke can vary with the nature of a feed, the desired severity of a visbreaking process can vary based on the feed. In some aspects, the severity of visbreaking that can be performed without resulting in coking can be increased by adding a donor solvent to the visbreaking environment.
[0055] In most hydrocarbon processes, there is a tradeoff between reaction temperature and residence time of reactants. Because visbreaking is a well-known and widely practiced process,
- 15 -Date Recue/Date Received 2020-09-03 however, correlations have been developed so that it is possible to express precisely the severity of the visbreaking process. An expression of the "severity" of a particular visbreaking operation does not mean that a certain degree of conversion can be predicted or obtained or that a certain amount of coke or sediment will be formed; rather it means that it is possible to predict that if all other reaction parameters are unchanged (e.g., feed composition, reactor pressure) except for the temperature and residence time in the reactor, two operations can be compared and it can be determined whether one process is more severe than the other. Equations and tables have been developed for comparing reaction severities. Typical of such presentations is the discussion of "soaking factor" in Petroleum Refinery Engineering¨Thermocracking and Decomposition Process--Equation 19-23 and Table 19-18, in Nelson--Modern Refining Technology, Chapter 19. The "soaking factor" corresponds to the severity index as defined above.
100561 In this discussion, severity index refers to the severity of the operation, expressed as the equivalent number of seconds of residence time in a reactor operating at 427 C
(800 F). It is noted that other definitions of severity index are possible based on different temperatures of operation. In very general terms, the reaction rate doubles for every 12 C to 13 C increase in temperature. Thus, 60 seconds of residence time at 427 C is equivalent to a severity index of 60, and increasing the temperature to 456 C would make the operation five times as severe, i.e. a severity index of 300.
Expressed in another way, 300 seconds at 427 C is equivalent to 60 seconds at 456 C, and the same product mix and distribution should be obtained under either set of conditions.
100571 The visbreaking process conditions which may be used can vary widely based on the nature of the heavy oil material, the optional hydrogen-donor material and other factors. In general, the visbreaking can be carried out at temperatures ranging from 350 C to 485 C, preferably 400 C
to 440 C, at residence times ranging from 1 to 60 minutes, preferably 15 to 45 minutes. Expressed as severity index, the partial upgrading can be performed at a severity index of 250 to 5000, or 400 to 2500, or 250 to 2500, or 1000 to 2500, or 400 to 1000, or 250 to 1000, or 500 to 800. It is noted that these severity ranges correspond to severities for process conditions corresponding to various types of visbreaking, visbreaking in the presence of hydrogen and/or a hydrogen donor, and/or other types of milder partial upgrading. The severity for a partial upgrading process based on coking can correspond to a severity index greater than 5000.
100561 In this discussion, severity index refers to the severity of the operation, expressed as the equivalent number of seconds of residence time in a reactor operating at 427 C
(800 F). It is noted that other definitions of severity index are possible based on different temperatures of operation. In very general terms, the reaction rate doubles for every 12 C to 13 C increase in temperature. Thus, 60 seconds of residence time at 427 C is equivalent to a severity index of 60, and increasing the temperature to 456 C would make the operation five times as severe, i.e. a severity index of 300.
Expressed in another way, 300 seconds at 427 C is equivalent to 60 seconds at 456 C, and the same product mix and distribution should be obtained under either set of conditions.
100571 The visbreaking process conditions which may be used can vary widely based on the nature of the heavy oil material, the optional hydrogen-donor material and other factors. In general, the visbreaking can be carried out at temperatures ranging from 350 C to 485 C, preferably 400 C
to 440 C, at residence times ranging from 1 to 60 minutes, preferably 15 to 45 minutes. Expressed as severity index, the partial upgrading can be performed at a severity index of 250 to 5000, or 400 to 2500, or 250 to 2500, or 1000 to 2500, or 400 to 1000, or 250 to 1000, or 500 to 800. It is noted that these severity ranges correspond to severities for process conditions corresponding to various types of visbreaking, visbreaking in the presence of hydrogen and/or a hydrogen donor, and/or other types of milder partial upgrading. The severity for a partial upgrading process based on coking can correspond to a severity index greater than 5000.
- 16 -Date Recue/Date Received 2020-09-03 100581 The severity index for the partial upgrading can be selected, for example, in order to achieve a desired density and/or a desired kinematic viscosity for the partially upgraded product.
For example, the severity index can be selected to achieve an API gravity for the partially upgraded product of 14 or more, or 16 or more, or 18 or more, or 19 or more.
Additionally or alternately, the severity index can be selected to achieve a kinematic viscosity at 7.5 C
of 500 cSt or less, or 400 cSt or less, or 360 cSt or less, or 350 cSt or less.
100591 The limit of severity is determined primarily by product quality.
Visbreaking is a relatively inexpensive process, and once a visbreaker has been installed, it does not cost much more to run it at high severity in order to achieve the maximum viscosity reduction possible with a given feed stock. However, the two limiting factors in the visbreaker operation are the formation of coke (which tends to plug the coil and/or soaking drum used in the visbreaker and also take the product out of specification) and sediment formation in the product. Sediment formation is a complicated phenomenon. As a generalization, it can be stated that, if the composition of an oil is changed enough, the asphaltic materials may no longer dissolve in the product and hence settle out as sediment. The problem becomes worse when cutter stocks or blending stocks of a less aromatic nature are added to the visbreaker product; the asphaltics or other materials that would remain dissolved in the visbreaker product are no longer soluble upon blending the visbreaker product with other, less aromatic materials.
100601 The pressure employed in a visbreaker can usually be sufficient to maintain most of the material in the reactor coil and/or soaker drum in the liquid phase. Normally the pressure is not considered as a control variable, although attempts are made to keep the pressure high enough to maintain most of the material in the visbreaker in the liquid phase. Some vapor formation in the visbreaker is not harmful, and is frequently inevitable because of the production of some light ends in the visbreaking process. Some coil visbreaker units operate with 20-40%
vaporization material at the visbreaker coil outlet. Lighter solvents will vaporize more and the vapor will not do much good towards improving the processing of the liquid phase material. Accordingly, liquid phase operation is preferred, but significant amounts of vaporization can be tolerated.
100611 In general, the pressures commonly encountered in visbreakers range from 170 to 10450 kPa, or 1480 to 8500 kPa. Such pressures will usually be sufficient to maintain liquid phase conditions and the desired degree of conversion.
For example, the severity index can be selected to achieve an API gravity for the partially upgraded product of 14 or more, or 16 or more, or 18 or more, or 19 or more.
Additionally or alternately, the severity index can be selected to achieve a kinematic viscosity at 7.5 C
of 500 cSt or less, or 400 cSt or less, or 360 cSt or less, or 350 cSt or less.
100591 The limit of severity is determined primarily by product quality.
Visbreaking is a relatively inexpensive process, and once a visbreaker has been installed, it does not cost much more to run it at high severity in order to achieve the maximum viscosity reduction possible with a given feed stock. However, the two limiting factors in the visbreaker operation are the formation of coke (which tends to plug the coil and/or soaking drum used in the visbreaker and also take the product out of specification) and sediment formation in the product. Sediment formation is a complicated phenomenon. As a generalization, it can be stated that, if the composition of an oil is changed enough, the asphaltic materials may no longer dissolve in the product and hence settle out as sediment. The problem becomes worse when cutter stocks or blending stocks of a less aromatic nature are added to the visbreaker product; the asphaltics or other materials that would remain dissolved in the visbreaker product are no longer soluble upon blending the visbreaker product with other, less aromatic materials.
100601 The pressure employed in a visbreaker can usually be sufficient to maintain most of the material in the reactor coil and/or soaker drum in the liquid phase. Normally the pressure is not considered as a control variable, although attempts are made to keep the pressure high enough to maintain most of the material in the visbreaker in the liquid phase. Some vapor formation in the visbreaker is not harmful, and is frequently inevitable because of the production of some light ends in the visbreaking process. Some coil visbreaker units operate with 20-40%
vaporization material at the visbreaker coil outlet. Lighter solvents will vaporize more and the vapor will not do much good towards improving the processing of the liquid phase material. Accordingly, liquid phase operation is preferred, but significant amounts of vaporization can be tolerated.
100611 In general, the pressures commonly encountered in visbreakers range from 170 to 10450 kPa, or 1480 to 8500 kPa. Such pressures will usually be sufficient to maintain liquid phase conditions and the desired degree of conversion.
- 17 -Date Recue/Date Received 2020-09-03 100621 In some aspects, a hydrogen donor solvent can be used. In a partial upgrading environment, a suitable donor solvent can be a recycled portion of the partially upgraded effluent, such as a recycled distillate portion and/or a recycled vacuum gas oil portion. If a hydrogen donor solvent is used, the hydrogen donor solvent can correspond to 0.1 wt% to 50 wt% of the total flow into the visbreaker.
100631 In some aspects, the visbreaking can be performed in the presence of hydrogen gas. In such aspects, the visbreaking can be performed in the presence of hydrogen partial pressures ranging from 0.4 MPa-g to 13.9 MPa-g (-50 to ¨2000 psig) and treat gas rates of from 89 m3/m3 to 890 m3/m3 (-500 to ¨5000 scf/B).
100641 In other aspects, any convenient type of partial upgrading can be performed. For example, if slurry hydrocracking or another type of hydroprocessing is used, the desired goals of partial upgrading can be similar. Thus, the hydroprocessing conditions can be selected to achieve an API gravity of 14 or more, or 16 or more, or 18 or more, or 19 or more and/or a kinematic viscosity at 7.5 C of 500 cSt or less, or 400 cSt or less, or 360 cSt or less, or 350 cSt or less. This can correspond to, for example, performing partial upgrading with total conversion relative to 566 C
of 40 wt% to 90 wt%, or 40 wt% to 70 wt%, or 70 wt% to 90 wt%.
100651 When numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated. While the illustrative embodiments of the invention have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.
100661 The present invention has been described above with reference to numerous embodiments and specific examples. Many variations will suggest themselves to those skilled in this art in light of the above detailed description. All such obvious variations are within the full intended scope of the appended claims.
100631 In some aspects, the visbreaking can be performed in the presence of hydrogen gas. In such aspects, the visbreaking can be performed in the presence of hydrogen partial pressures ranging from 0.4 MPa-g to 13.9 MPa-g (-50 to ¨2000 psig) and treat gas rates of from 89 m3/m3 to 890 m3/m3 (-500 to ¨5000 scf/B).
100641 In other aspects, any convenient type of partial upgrading can be performed. For example, if slurry hydrocracking or another type of hydroprocessing is used, the desired goals of partial upgrading can be similar. Thus, the hydroprocessing conditions can be selected to achieve an API gravity of 14 or more, or 16 or more, or 18 or more, or 19 or more and/or a kinematic viscosity at 7.5 C of 500 cSt or less, or 400 cSt or less, or 360 cSt or less, or 350 cSt or less. This can correspond to, for example, performing partial upgrading with total conversion relative to 566 C
of 40 wt% to 90 wt%, or 40 wt% to 70 wt%, or 70 wt% to 90 wt%.
100651 When numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated. While the illustrative embodiments of the invention have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.
100661 The present invention has been described above with reference to numerous embodiments and specific examples. Many variations will suggest themselves to those skilled in this art in light of the above detailed description. All such obvious variations are within the full intended scope of the appended claims.
- 18 -Date Recue/Date Received 2020-09-03
Claims (34)
1. A method for upgrading a heavy hydrocarbon feed, comprising:
subjecting a heavy hydrocarbon feedstock comprising an API gravity of 16 or less and kinematic viscosity at 7.5°C of 500 c St or more to a partial upgrading process to form a partially processed effluent comprising 1.1 wt% or more of olefins;
separating, from the partially processed effluent, a first fraction comprising a T95 distillation point of 750°F (400°C) or less and a second fraction comprising a higher T95 distillation point than the first fraction, the first fraction comprising a weight percentage of olefms that is greater than the weight percentage of olefms in the partially processed effluent;
subjecting at least a portion of the first fraction to a reforming process to form at least a reformed fraction comprising less than 1.0 wt% olefins and a hydrogen-containing fraction;
blending at least a portion of the reformed fraction with the second fraction to form a partially upgraded product comprising an API gravity of 14 or more and a kinematic viscosity at 7.5 cSt of 500 c St or less.
subjecting a heavy hydrocarbon feedstock comprising an API gravity of 16 or less and kinematic viscosity at 7.5°C of 500 c St or more to a partial upgrading process to form a partially processed effluent comprising 1.1 wt% or more of olefins;
separating, from the partially processed effluent, a first fraction comprising a T95 distillation point of 750°F (400°C) or less and a second fraction comprising a higher T95 distillation point than the first fraction, the first fraction comprising a weight percentage of olefms that is greater than the weight percentage of olefms in the partially processed effluent;
subjecting at least a portion of the first fraction to a reforming process to form at least a reformed fraction comprising less than 1.0 wt% olefins and a hydrogen-containing fraction;
blending at least a portion of the reformed fraction with the second fraction to form a partially upgraded product comprising an API gravity of 14 or more and a kinematic viscosity at 7.5 cSt of 500 c St or less.
2. The method of claim 1, wherein the heavy hydrocarbon feedstock comprises a bitumen.
3. The method of claim 1 or 2, wherein the partial upgrading process comprises a severity index of 1000 or less.
4. The method of claim 1 or 2, wherein the partial upgrading process comprises 70 wt% or less total conversion relative to 566°C, or wherein the partial upgrading process comprises greater than 70 wt% total conversion relative to 566°C.
5. The method of any one of claims 1 ¨ 4, wherein the partially processed effluent comprises 2.0 wt% or more of olefins.
6. The method of any one of claims 1 ¨ 5, wherein subjecting the heavy hydrocarbon feedstock or the at least a portion of the heavy feedstock fraction to the partial upgrading process comprises subjecting the heavy hydrocarbon feedstock or the at least a portion of the heavy feedstock fraction to the partial upgrading process in the presence of at least a portion of the hydrogen-containing stream.
7. The method of any one of claims 1 ¨ 6, wherein subjecting at least a portion of the first fraction to a reforming process further comprises forming a fuel gas fraction.
8. The method of claim 7, wherein at least a portion of the fuel gas fraction is combusted to provide heat for the partial upgrading conditions.
9. The method of any one of claims 1 ¨ 8, wherein the first fraction comprises a T80 distillation point of 260 C or more.
10. The method of any one of claims 1 ¨ 9, wherein the first fraction comprises a T95 distillation point of 260 C or less.
11. The method of any one of claims 1 ¨ 10, wherein the first fraction comprises a T5 distillation point of 30 C or more and a T95 distillation point of 205 C or less.
12. The method of any one of claims 1 ¨ 11, wherein the reformed fraction comprises 0.5 wt% or less olefms.
13. The method of any one of claims 1 ¨ 12, wherein the partially upgraded product comprises a kinematic viscosity at 7.5 C that is at least 10 cSt lower than a kinematic viscosity of the partially processed effluent.
14. The method of any one of claims 1 ¨ 13, wherein the heavy hydrocarbon feedstock or the initial feedstock comprises a bitumen formed by a paraffinic froth treatment process, a naphtha froth treatment, a cyclic steam stimulation (CSS) process, a liquid addition to steam to enhance recovery (LASER) process, a steam-assisted gravity drainage process (SAGD), solvent-assisted steam-assisted gravity drainage (SA-SAGD) process, a heated vapor extraction (VAPEX) process, a cyclic solvent process (CSP), or a combination thereof.
Date Recue/Date Received 2022-02-02
Date Recue/Date Received 2022-02-02
15. The method of any one of claims 1 ¨ 14, wherein the partial upgrading process comprises visbreaking, visbreaking in the presence of a hydrogen donor solvent, visbreaking in the presence of hydrogen, sodium desulfurization, or a combination thereof.
16. The method of any one of claims 1 ¨ 14, wherein the partial upgrading process comprises a thermal upgrading process.
17. The method of any one of claims 1 ¨ 14, wherein the partial upgrading process comprises slurry hydroprocessing, ebullated bed hydroprocessing, or a combination thereof.
18. A method for upgrading a feedstock, comprising:
separating an initial feedstock comprising an API gravity of 16 or less and a kinematic viscosity at 7.5 C of 500 c St or more to form at least a light feedstock fraction comprising a T95 distillation point of 500 C or less and a heavy feedstock fraction comprising a T50 distillation point greater than 500 C;
subjecting at least a portion of the heavy feedstock fraction to a partial upgrading process to form a partially processed effluent comprising 1.1 wt% or more of olefins;
separating, from the partially processed effluent, a first fraction comprising a T95 distillation point of 750 F (-400 C) or less and a second fraction comprising a higher T95 distillation point than the first fraction, the first fraction comprising a weight percentage of olefms that is greater than the weight percentage of olefms in the partially processed effluent;
subjecting at least a portion of the first fraction and at least a portion of the light feedstock fraction to a reforming process to form at least a reformed fraction comprising less than 1.0 wt% olefins and a hydrogen-containing fraction;
blending at least a portion of the reformed fraction with the second fraction to form a partially upgraded product comprising an API gravity of 14 or more and a kinematic viscosity at 7.5 cSt of 500 c St or less.
Date Recue/Date Received 2022-02-02
separating an initial feedstock comprising an API gravity of 16 or less and a kinematic viscosity at 7.5 C of 500 c St or more to form at least a light feedstock fraction comprising a T95 distillation point of 500 C or less and a heavy feedstock fraction comprising a T50 distillation point greater than 500 C;
subjecting at least a portion of the heavy feedstock fraction to a partial upgrading process to form a partially processed effluent comprising 1.1 wt% or more of olefins;
separating, from the partially processed effluent, a first fraction comprising a T95 distillation point of 750 F (-400 C) or less and a second fraction comprising a higher T95 distillation point than the first fraction, the first fraction comprising a weight percentage of olefms that is greater than the weight percentage of olefms in the partially processed effluent;
subjecting at least a portion of the first fraction and at least a portion of the light feedstock fraction to a reforming process to form at least a reformed fraction comprising less than 1.0 wt% olefins and a hydrogen-containing fraction;
blending at least a portion of the reformed fraction with the second fraction to form a partially upgraded product comprising an API gravity of 14 or more and a kinematic viscosity at 7.5 cSt of 500 c St or less.
Date Recue/Date Received 2022-02-02
19. The method of claim 18, wherein the T95 distillation point of the light feedstock fraction is 400°C or less, or wherein the initial feedstock comprises a bitumen feedstock, or a combination thereof.
20. The method of claim 18 or 19, wherein the partial upgrading process comprises a severity index of 1000 or less.
21. The method of claim 18 or 19, wherein the partial upgrading process comprises 70 wt%
or less total conversion relative to 566°C, or wherein the partial upgrading process comprises greater than 70 wt% total conversion relative to 566°C.
or less total conversion relative to 566°C, or wherein the partial upgrading process comprises greater than 70 wt% total conversion relative to 566°C.
22. The method of any one of claims 18 ¨ 21, wherein the partially processed effluent comprises 2.0 wt% or more of olefms.
23. The method of any one of claims 18 ¨ 22, wherein subjecting the heavy hydrocarbon feedstock or the at least a portion of the heavy feedstock fraction to the partial upgrading process comprises subjecting the heavy hydrocarbon feedstock or the at least a portion of the heavy feedstock fraction to the partial upgrading process in the presence of at least a portion of the hydrogen-containing stream.
24. The method of any one of claims 18 ¨ 23, wherein subjecting at least a portion of the first fraction to a reforming process further comprises forming a fuel gas fraction.
25. The method of claim 24, wherein at least a portion of the fuel gas fraction is combusted to provide heat for the partial upgrading conditions.
26. The method of any one of claims 18 ¨ 25, wherein the first fraction comprises a T80 distillation point of 260°C or more.
27. The method of any one of claims 18 ¨ 26, wherein the first fraction comprises a T95 distillation point of 260°C or less.
28. The method of any one of claims 18 ¨ 27, wherein the first fraction comprises a T5 distillation point of 30 C or more and a T95 distillation point of 205 C or less.
29. The method of any one of claims 18 ¨ 28, wherein the reformed fraction comprises 0.5 wt% or less olefins.
30. The method of any one of claims 18 ¨ 29, wherein the partially upgraded product comprises a kinematic viscosity at 7.5 C that is at least 10 c St lower than a kinematic viscosity of the partially processed effluent.
31. The method of any one of claims 18 ¨ 30, wherein the heavy hydrocarbon feedstock or the initial feedstock comprises a bitumen formed by a paraffinic froth treatment process, a naphtha froth treatment, a cyclic steam stimulation (CSS) process, a liquid addition to steam to enhance recovery (LASER) process, a steam-assisted gravity drainage process (SAGD), solvent-assisted steam-assisted gravity drainage (SA-SAGD) process, a heated vapor extraction (VAPEX) process, a cyclic solvent process (CSP), or a combination thereof.
32. The method of any one of claims 18 ¨ 31, wherein the partial upgrading process comprises visbreaking, visbreaking in the presence of a hydrogen donor solvent, visbreaking in the presence of hydrogen, sodium desulfurization, or a combination thereof.
33. The method of any one of claims 18 ¨ 31, wherein the partial upgrading process comprises a thermal upgrading process.
34. The method of any one of claims 18 ¨ 31, wherein the partial upgrading process comprises slurry hydroprocessing, ebullated bed hydroprocessing, or a combination thereof.
Date Recue/Date Received 2022-02-02
Date Recue/Date Received 2022-02-02
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