阅读说明：本技术 由三产物脱沥青形成沥青馏分 (Deasphalting of three products to form an asphalt fraction ) 是由 基斯·K·奥尔德斯 卡莫尔·布萨迪 肯德尔·S·福如奇 萨拉·K·格林 于 2018-07-10 设计创作，主要内容包括：本发明提供了使用三产物脱沥青装置生产脱沥青油、树脂和残油的有利组合的系统和方法。脱沥青油、树脂和残油然后可以进一步合并,任选地与生成三产物脱沥青装置的进料的蒸馏期间产生的其它减压瓦斯油馏分一起,以产生质量改善的产物构成,同时也维持了所生成的沥青产物的质量并减少或最小化所生成的较低价值产物的量。通过顺序地脱沥青、通过使用树脂沉降器从脱沥青油中分离树脂、或通过任何其它便利的方法,可以由三产物脱沥青装置生成额外的“树脂”产物。(The present invention provides a system and method for producing an advantageous combination of deasphalted oil, resin and resid using a three-product deasphalting unit. The deasphalted oil, resin and resid can then be further combined, optionally with other vacuum gas oil fractions produced during distillation of the feed to the three-product deasphalting unit, to produce a product slate of improved quality while also maintaining the quality of the produced asphalt product and reducing or minimizing the amount of lower value products produced. Additional "resin" products may be produced by the three-product deasphalting unit by sequential deasphalting, by separating the resin from the deasphalted oil using a resin settler, or by any other convenient method.)

1. A method for processing a heavy oil fraction, the method comprising:

separating a vacuum gas oil fraction and a vacuum residue fraction from a heavy oil feed;

under the first solvent deasphalting conditions, using C₄₊Solvent deasphalting at least a portion of the vacuum residuum fraction to produceFirst deasphalted oil and first deasphalting unit residue, effective solvent deasphalting conditions producing a yield of first deasphalted oil of 50% or greater by weight of the feedstock;

solvent deasphalting at least a portion of the first deasphalted oil under second solvent deasphalting conditions to form a second deasphalted oil and a second deasphalting unit resin, the second solvent deasphalting conditions comprising deasphalting conditions having a degree of lift lower than the first solvent deasphalting conditions;

formed from at least a portion of a) the vacuum gas oil fraction, b) the first deasphalting unit residue, c) the second deasphalting oil, and d) the second deasphalting unit resin forming products comprising an asphalt fraction and one or more fuel feeds, lubricating oil feeds, or combinations thereof, in a volume of 95 volume percent or more, or 98 volume percent or more of the combined volume of the vacuum gas oil fraction and the vacuum residue fraction;

further processing the one or more fuel feeds, lubricating oil feeds, or compositions thereof, the further processing comprising hydroprocessing, fluid catalytic cracking, or combinations thereof; and

incorporating the bitumen fraction into a bitumen product.

2. The process of claim 1, wherein the second deasphalting conditions comprise a deasphalting solvent having a smaller number of carbon atoms per molecule than the deasphalting solvent of the first deasphalting conditions; or wherein the second deasphalting conditions comprise a temperature higher than the first deasphalting conditions; or a combination thereof.

3. The method of any of the above claims, wherein the yield of the first deasphalted oil is 60 wt% or greater, or 70 wt% or greater.

4. The process of any of the preceding claims, wherein the product comprises a product formed from at least a portion of the first deasphalted oil, at least a portion of the vacuum residue, or a combination thereof.

5. A method for processing a heavy oil fraction, the method comprising:

separating a vacuum gas oil fraction and a vacuum residue fraction from a heavy oil feed;

solvent deasphalting at least a portion of the vacuum residue fraction under first solvent deasphalting conditions to produce a first deasphalted oil and a first deasphalting unit residue, the effective solvent deasphalting conditions producing a yield of the first deasphalted oil of 50 wt.% or greater of the feedstock;

under the second solvent deasphalting conditions, using C₄₊Solvent deasphalting at least a portion of the first deasphalting unit residue with a solvent to form a second deasphalting unit residue and a second deasphalting unit resin, the second solvent deasphalting conditions comprising a severity lower than the first solvent deasphalting conditions;

formed from at least a portion of a) the vacuum gas oil fraction, b) the second deasphalting unit residue, c) the first deasphalting oil, and d) the second deasphalting unit resin forming products comprising an asphalt fraction and one or more fuel feeds, lubricating oil feeds, or combinations thereof, in a volume of 95 volume percent or more, or 98 volume percent or more of the combined volume of the vacuum gas oil fraction and the vacuum residue fraction;

further processing the one or more fuel feeds, lubricating oil feeds, or compositions thereof, the further processing comprising hydroprocessing, fluid catalytic cracking, or combinations thereof; and

incorporating the bitumen fraction into a bitumen product.

6. The process of claim 5, wherein the second deasphalting conditions comprise a deasphalting solvent having a greater number of carbon atoms per molecule than the deasphalting solvent of the first deasphalting conditions; or wherein said second deasphalting conditions comprise a temperature lower than said first deasphalting conditions; or a combination thereof.

7. The process of claim 5 or 6, wherein the product comprises a product formed from at least a portion of the first deasphalting unit residue, at least a portion of the vacuum residue, or a combination thereof.

8. The process of any of the above claims, wherein the bitumen fraction is incorporated into the bitumen product without subjecting the bitumen fraction to thermal cracking conditions.

9. The process of any of the preceding claims, wherein the product constitutes a volume that is 105 vol% or less, or 102 vol% or less of the combined volume of the vacuum gas oil fraction and the vacuum residue fraction.

10. The process of any of the above claims, wherein the product slate further comprises a fuel oil fraction.

11. The process of any one of the preceding claims, wherein the vacuum gas oil fraction has a T10 cut point of 482 ℃ or greater, or 510 ℃ or greater.

12. The method of any of the above claims, wherein the one or more of the fuel feed, the lubricating oil feed, or a combination thereof comprises a conradson carbon content of 10 wt.% or less, or 8.0 wt.% or less, or 6.0 wt.% or less; or wherein the one or more of a fuel feed, a lubricating oil feed, or a combination thereof has an API gravity of 14 or greater, or 16 or greater; or a combination thereof.

13. The process of any of the preceding claims, where the asphalt fraction comprises at least a portion of the second deasphalting unit resin, the process further comprising blowing the asphalt fraction.

14. A product formation formed according to the method of any one of the preceding claims.

15. An asphalt composition formed by a process comprising blowing an asphalt fraction comprising a deasphalting unit resin having a kinematic viscosity at 100 ℃ of 5000cSt or greater.

Technical Field

Systems and methods for producing asphalt and fuel products from deasphalter (deasphalter) resid and deasphalter resins are provided.

Background

Conventionally, crude oil is often described as being made up of multiple boiling ranges. The lower boiling range compounds in crude oil are equivalent to naphtha or kerosene fuels. The mid boiling range distillate compounds can be used as diesel fuel or as lubricating oil base stocks. If any higher boiling range compounds are present in the crude oil, such compounds are considered to be residual or "resid" compounds, corresponding to the portion of the crude oil remaining after atmospheric and/or vacuum distillation of the crude oil.

Solvent deasphalting is a common refinery process used to process defective and/or heavy oil feeds, such as residual fractions produced after crude distillation. Conventional solvent deasphalting configurations can be used to convert a heavy oil feed into a deasphalted oil fraction and a deasphalter residue or "resid" fraction. Unfortunately, it can be difficult to achieve the desired product quality for both the deasphalted oil and the resid. One of the main objectives of solvent deasphalting may be to upgrade defective fractions, such as vacuum residuum, to deasphalted oils. The deasphalted oil can then be suitable for processing to form, for example, a lubricating oil base oil or distillate fuel. However, conducting solvent deasphalting to form an upgraded deasphalted oil may tend to result in the formation of a residue fraction that is incompatible with vacuum gas oil blending. This incompatibility can pose a challenge in finding high value end uses for the produced resid fraction.

Some configurations for conducting deasphalting to form three deasphalted products are also known. The third product generally corresponds to a product of intermediate quality with respect to deasphalted oil and residual oil. This intermediate product may be referred to as a resin product.

U.S. patent 9,296,959 and U.S. patent application publication 2013/0026063 describe configurations for performing solvent deasphalting to form deasphalted oil products, resin products, and asphalt products. The resin product is formed by passing the deasphalted oil through a resin settler. The deasphalting solvent is then removed from the resin product and the deasphalted oil product, respectively. Additional resin product formation is described as being beneficial to reduce the severity required for hydroprocessing the deasphalted oil product and/or to reduce the amount of coke formed during further processing of the pitch product.

It would be beneficial to find other strategies for processing defective fractions that can achieve increased yields of higher value products while maintaining the desired product quality of the produced products.

Disclosure of Invention

In various aspects, methods for processing heavy oil fractions are provided. The process includes separating a vacuum gas oil fraction and a vacuum residue fraction from a heavy oil feed. At least a portion of the vacuum residue fraction is then solvent deasphalted under first solvent deasphalting conditions to produce a first deasphalted oil and a first deasphalting unit residue. In some aspects, the first solvent deasphalting conditions can correspond to higher lift (lift) deasphalting conditions, wherein the effective solvent deasphalting conditions produce a first deasphalted oil yield of 50 weight percent or greater of the feedstock. In other aspects, the first solvent deasphalting conditions can correspond to lower degree of upgrade deasphalting conditions. And then carrying out a second solvent deasphalting process under second solvent deasphalting conditions. And if the degree of improvement of the second solvent deasphalting conditions is lower than the first solvent deasphalting conditions, performing second solvent deasphalting on the first deasphalted oil. And if the promotion degree of the second solvent deasphalting conditions is higher than the first solvent deasphalting conditions, performing second solvent deasphalting on the residue of the first deasphalting device. The change in degree of lift between the first deasphalting conditions and the second deasphalting conditions can be achieved in any convenient manner, for example by changing the nature of the solvent or changing the temperature during deasphalting. Product slate may then be formed. If the degree of upgrade of the second solvent deasphalting conditions is lower than the first solvent deasphalting conditions, a product slate may be formed from at least a portion of a) the vacuum gas oil fraction, b) the first deasphalting unit residue, c) the second deasphalting oil, and d) the second deasphalting unit resin. If the degree of upgrade of the second solvent deasphalting conditions is higher than the first solvent deasphalting conditions, a product slate may be formed from at least a portion of a) the vacuum gas oil fraction, b) the second deasphalting unit residue, c) the first deasphalting oil, and d) the second deasphalting unit resin. The product slate can include an asphalt fraction and one or more of a fuel feed, a lubricating oil feed, or a combination thereof. The product may constitute a volume corresponding to 95 vol% or more, or 98 vol% or more, and/or 105 vol% or less, or 102 vol% or less of the combined volume of the vacuum gas oil fraction and the vacuum residue fraction. The one or more fuel feeds, lubricating oil feeds, or compositions thereof may then be subjected to further processing, including hydroprocessing, fluid catalytic cracking, or combinations thereof. The bitumen fraction may be incorporated into the bitumen product, optionally after air blowing. The bitumen fraction may optionally, but preferably, be incorporated into the bitumen product without subjecting the bitumen fraction to thermal cracking conditions.

In such aspects, separation using a three-product deasphalting unit can result in an increase in the amount of product in the product slate that is suitable for use as a feed for distillate fuel and/or lube oil production or for the pitch product. Thereby, the amount of fuel oil fractions and/or residual oil fractions unsuitable for incorporation into asphalt can be reduced or minimized.

In some aspects, the vacuum gas oil fraction may have a T10 cut point of 482 ℃ or greater, or 510 ℃ or greater. In some aspects, the one or more fuel feeds, lubricating oil feeds, or compositions thereof can comprise a Conradson carbon content of 10 wt.% or less, or 8.0 wt.% or less, or 6.0 wt.% or less. In some aspects, the one or more fuel feeds, lubricating oil feeds, or combinations thereof have an API gravity of 14 or greater, or 16 or greater.

In some aspects, the pitch fraction may comprise at least a portion of the second deasphalting unit resin. In such an aspect, the method may further comprise blowing the bitumen fraction.

In various aspects, asphalt compositions are also provided. The asphalt composition may be formed by blowing an asphalt fraction comprising deasphalting unit resins having a kinematic viscosity at 100 ℃ of 5000cSt or greater.

Drawings

FIG. 1 herein is a process flow diagram of a pitch oxidation process.

FIG. 2 herein is a process flow diagram of a pitch oxidation process.

Fig. 3 schematically shows an example of the configuration of a three-product deasphalting apparatus based on sequential deasphalting.

Detailed Description

All numbers in the description and claims herein are to be modified by the term "about" or "approximately" in view of experimental error and variations that would be expected by a person of ordinary skill in the art.

SUMMARY

In various aspects, systems and methods are provided for producing advantageous combinations of deasphalted oil, resin, and residual oil (rock) using a three-product deasphalting unit. The deasphalted oil, resin and resid can then be further combined, optionally with other vacuum gas oil fractions produced during distillation of the feed to the three-product deasphalting unit, to produce a product slate of improved quality while also maintaining the quality of the produced asphalt product and reducing or minimizing the amount of lower value products produced. Additional "resin" products may be generated from the three-product deasphalting unit by sequential deasphalting, by separating the resin from the deasphalted oil using a resin settler, or by any other convenient method.

Additionally or alternatively, a three-product deasphalting unit can be used to produce a heavy resin product, such as a resin product having a kinematic viscosity at 100 ℃ of approximately 5000cSt or greater. The heavy resin product may be combined with vacuum gas oil and/or deasphalted oil and used to form commercial grade bitumen after air blowing. Optionally, vacuum residuum and/or resid may also be combined with heavy resins to form commercial grade bitumen.

As an example of sequential deasphalting, a deasphalting process can be performed to form a first deasphalted oil and a residual oil. The first deasphalted oil may then be subjected to a second deasphalting process under deasphalting conditions corresponding to deasphalting conditions "less elevated" than the first deasphalting conditions. This may result in a second deasphalted oil and a residual fraction corresponding to the resin fraction. The resin fraction may represent a fraction that would traditionally be included as part of the deasphalting unit resid fraction (i.e., if a single deasphalting stage is used at lower degrees of lift). However, because sequential deasphalting is performed, the resin fraction can be obtained as a separate fraction that can be blended and/or further processed to form a higher value product. In some aspects, the yield of the second deasphalted oil relative to the overall yield of the initial feed may be similar to the yield of a single stage deasphalting process under lower degree of upgrading deasphalting conditions. As one example of sequential deasphalting, a first deasphalting process may correspond to hexane deasphalting, while a second deasphalting process may correspond to pentane deasphalting. As another example, the first deasphalting process may correspond to pentane deasphalting, while the second deasphalting process may correspond to propane deasphalting. In some aspects, the first deasphalting stage during sequential deasphalting can include deasphalting conditions that produce a deasphalted oil yield (i.e., degree of upgrade) of 50 wt% or greater, or 60 wt% or greater, or 70 wt% or greater.

FIG. 3 shows an example of a sequential deasphalting configuration. In fig. 3, the elements within the dotted area correspond to the elements of the sequential deasphalting unit. In fig. 3, feed 305 is introduced into a first deasphalting section 310. The first deasphalting section 310 produces a first deasphalted oil 315 and a resid fraction 317. The first deasphalted oil 315 then enters the second deasphalting stage 320. Second deasphalting stage 320 produces a second deasphalted oil 325 and a resin fraction 327. It is noted that the configuration shown in fig. 3 shows the period of the sequential deasphalting process to form a resin fraction having a high kinematic viscosity at 100 ℃.

As another alternative, sequential deasphalting may be performed such that the first deasphalting process is a lower degree of lift process. This can result in the formation of deasphalted oil and deasphalter bottoms. The deasphalting unit bottoms can then be subjected to a second deasphalting process using a second solvent that can provide a higher degree of lift during deasphalting. The products from the second deasphalting unit process can be resinous products and resids.

Another option for forming the resin fraction may be to use a resin settler to separate the resin fraction from the deasphalted oil. During solvent deasphalting, the feed (e.g., vacuum residuum fraction) is mixed with a suitable solvent. This results in phase separation to form a first phase corresponding to the deasphalted oil plus a major portion of the solvent and a second phase corresponding to the deasphalting unit residue or resid plus a minor portion of the solvent. If only two products are desired, the solvent can be removed from the deasphalted oil to form a deasphalted oil product. If additional resin product is desired, a resin settler can be used to separate the resin from the deasphalted oil before the solvent is separated from the deasphalted oil. The resin may be formed by allowing the heavier portion of the deasphalted oil to settle (e.g., based on gravity or centrifugal force) to form a separate resin phase. The temperature of the solvent/deasphalted oil mixture can also be adjusted generally to further facilitate the separation of heavier and/or slightly soluble compounds from the deasphalted oil to form the resin. After the deasphalted oil is separated from the resin, both the deasphalted oil and the resin may undergo further separation to remove the deasphalting solvent from the deasphalted oil and the resin.

After three products are produced during deasphalting, these three products can be used to form a product slate that meets multiple objectives. In particular, the products that can be formed constitute the achievement: a) improved quality of high value fuel or lubricating oil feed; b) maintaining the quality of the bitumen product, and c) reducing or minimizing the production of fuel oil, which is required to find disposal of the total deasphalting unit product.

Additionally or alternatively, the production of the resin product may provide other options for forming a pitch product, such as producing pitch by blowing.

In this discussion, when comparing two sets of deasphalting conditions, the deasphalting conditions can be described based on the relative degree of enhancement or yield of the deasphalting process. Solvent deasphalting processes typically form a first product having a higher solubility in the solvent and a second product corresponding to a residual product having a lower solubility in the solvent. The "degree of upgrade" or yield of a deasphalting process generally corresponds to the amount of first product (dissolved in solvent) produced during solvent deasphalting. Thus, "higher degree of upgrade" deasphalting conditions refer to solvent deasphalting conditions that result in higher amounts of first product and correspondingly lower amounts of residual product. In general, the use of a deasphalting solvent with a higher number of carbon atoms per molecule will correspond to higher degree of deasphalting conditions. For example, using C₅Solvent deasphalting process of the solvent generally corresponds to the use of C₃The solvent deasphalting process of the solvent has higher promotion degree. Another example of a change in conditions that can result in a higher degree of deasphalting unit boost or yield is to perform the deasphalting process at a lower temperature.

Raw materials

In various aspects, at least a portion of the feedstock for processing as described herein may correspond to a vacuum resid fraction or other type of 950 ° f + (510 ℃ +), or 1000 ° f + (538 ++) fraction, or 1050 ° f + (566 ℃ +) fraction. Another example of a process for forming a 950F. + (510℃. +) fraction, or a 1000F. + (538℃. +) fraction, or a 1050F. + (566℃. +) fraction, is to perform a high temperature flash separation. The 950 ° f + (510 ℃ +), 1000 ° f + (538 ℃ +) or 1050 ° f + (566 ℃ +) fractions formed from high temperature flash may be processed in a manner similar to vacuum resid.

The vacuum resid fraction or a 510℃ + fraction (either 538℃ + fraction or 566℃ + fraction) formed from another process (e.g., flash fractionating bottoms or asphalt fraction) can be deasphalted with a high degree of lift to form a deasphalted oil. Optionally, the feedstock may also comprise a portion of a conventional feed for lubricant base stock production, such as vacuum gas oil.

The vacuum resid (or other 510 ℃ +/538 ℃ +/566 ℃ +) fraction may correspond to a fraction having a T5 cut point (ASTM D2892, or ASTM D7169 if the fraction cannot be completely eluted from the chromatographic system) of 900 ° F (482 ℃) or greater, or 950 ° F (510 ℃) or greater, or 1000 ° F (538 ℃) or greater. Alternatively, the vacuum residue fraction may be characterized on the basis of a T10 cut point (ASTM D2892/D7169) of 900 ° F (482 ℃) or greater, or 950 ° F (510 ℃) or greater, or 1000 ° F (538 ℃) or greater.

The metal content of the resid (or other 510 c +) fraction can be high. For example, the total nickel, vanadium and iron content of the residue fraction may be high. In one aspect, the resid fraction can contain 0.00005 grams Ni/V/Fe per gram resid (50wppm) or greater, or 0.0002 grams Ni/V/Fe per gram resid (200wppm) or greater, based on the total elements of nickel, vanadium, and iron. In other aspects, the heavy oil can contain 500wppm or more of nickel, vanadium, and iron, such as up to 1000wppm or more.

Contaminants such as nitrogen and sulfur are commonly found in residual (or other 510 c +) fractions, often in organically bound form. The nitrogen content can range from about 50wppm to about 10,000wppm elemental nitrogen or higher, based on the total weight of the resid fraction. The sulfur content can range from 500wppm to 100,000wppm elemental sulfur or greater, or from 1000wppm to 50,000wppm, or from 1000wppm to 30,000wppm, based on the total weight of the resid fraction.

Another method for characterizing the residual (or other 510 c +) fraction is based on the Conradson Carbon Residue (CCR) of the feedstock. The conradson carbon residue of the residue fraction may be 5 wt% or more, for example 10 wt% or more, or 20 wt% or more. Additionally or alternatively, the conradson carbon residue of the residue fraction may be 50 wt% or less, such as 40 wt% or less or 30 wt% or less.

In some aspects, the vacuum gas oil fraction may be co-processed with a deasphalted oil. The vacuum gas oil can be combined with the deasphalted oil in various amounts ranging from 20 parts by weight deasphalted oil to 1 part vacuum gas oil (i.e., 20:1) to 1 part deasphalted oil to 1 part vacuum gas oil. In some aspects, the weight ratio of deasphalted oil to vacuum gas oil can be at least 1:1, or at least 1.5:1, or at least 2: 1. Typical (vacuum) gas oil fractions may include, for example, fractions from the T5 cut point to the T95 cut point of 650F. (343 ℃) to 1050F. (566 ℃), or 650F. (343 ℃) to 1000F. (538 ℃), or 650F. (343 ℃) to 950F. (510 ℃), or 650F. (343 ℃) to 900F. (482 ℃), or 700F. (370 ℃) to 1050F. (566 ℃), or 700F. (370 ℃) to 1000F. (538 ℃), or 700F. (370 ℃) to 950F. (510 ℃), or 700F. (370 ℃) to 900F. (482 ℃), or 750F. (399 ℃) to 1050F. (566 ℃, 750F.) (538 ℃) or 750F. (950F. (510 ℃) to 750F. (399 ℃) or 750F. (482 ℃) to 900F. (482 DEG F.) (900F.) (482 ℃). For example, a suitable vacuum gas oil fraction may have a T5 cut point of 343 ℃ or greater and a T95 cut point of 566 ℃ or less; or a T10 cut point of 343 ℃ or higher and a T90 cut point of 566 ℃ or lower; or a T5 cut point of 370 ℃ or more and a T95 cut point of 566 ℃ or less; or a T5 cut point of 343 ℃ or higher and a T95 cut point of 538 ℃ or lower. Optionally, the vacuum gas oil fraction may correspond to a heavy vacuum gas oil having a T10 cut point of 482 ℃ or more, or 510 ℃ or more.

Solvent deasphalting

Solvent deasphalting is a solvent extraction process. In some aspects, suitable solvents for high yield deasphalting processes as described herein include alkanes or other hydrocarbons (e.g., alkenes) containing 4 to 7 carbons per molecule or 5 to 7 carbons per molecule. Examples of suitable solvents include n-butane, isobutane, n-pentane, C₄₊Alkane, C₅₊Alkane, C₄₊Hydrocarbons, and C₅₊A hydrocarbon. In some aspects, suitable solvents for low yield deasphalting may include C₃Hydrocarbons, e.g. propane, or C₃And/or C₄A hydrocarbon. Examples of suitable solvents for low yield deasphalting include propane, n-butane, isobutane, n-pentane, C₃₊Alkane, C₄₊Alkane, C₃₊Hydrocarbons, and C₄₊A hydrocarbon.

In this discussion, C is included_nA (hydrocarbon) solvent is defined as a solvent consisting of at least 80 wt.%, or at least 85 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 98 wt.% of alkanes (hydrocarbons) having n carbon atoms. Similarly, contains C_n+A (hydrocarbon) solvent is defined as a solvent consisting of at least 80 wt.%, or at least 85 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 98 wt.% of alkanes (hydrocarbons) having n or more carbon atoms.

In this discussion, C is included_nThe solvent of alkane (hydrocarbon) is defined to include a case where the solvent corresponds to a single alkane (hydrocarbon) containing n carbon atoms (for example, n ═ 3, 4, 5, 6, 7) and a case where the solvent is composed of a mixture of alkanes (hydrocarbons) containing n carbon atoms. Similarly, contains C_n+The solvent of alkane (hydrocarbon) is defined to include a case where the solvent corresponds to a single alkane (hydrocarbon) containing n or more carbon atoms (for example, n ═ 3, 4, 5, 6, 7) and a case where the solvent corresponds to a mixture of alkanes (hydrocarbons) containing n or more carbon atoms. Thus, comprising C₄₊The solvent for the alkane may correspond to a solvent comprising n-butane; a solvent comprising n-butane and isobutane; a solvent corresponding to a mixture of one or more butane isomers and one or more pentane isomers; or any other convenient combination of alkanes containing 4 or more carbon atoms. Similarly, contains C₅₊The solvent of alkane is defined to include a solvent corresponding to a single alkane (hydrocarbon) or a solvent corresponding to a mixture of alkanes (hydrocarbons) having 5 or more carbon atoms. Alternatively, other types of solvents may be suitable, such as supercritical fluids. In various aspects, the solvent used for solvent deasphalting can consist essentially of hydrocarbons, such that at least 98 weight percent or at least 99 weight percent of the solvent corresponds to compounds containing only carbon and hydrogen. In a deasphalting solvent corresponding to C₄₊Aspect of the deasphalting solvent, said C₄₊The deasphalting solvent may comprise less than 15 wt%, or less than 10 wt%, or less than 5 wt% of propane and/or other C₃Hydrocarbons, or said C₄₊The deasphalting solvent may be substantially free ofContaining propane and/or other C₃Hydrocarbons (less than 1 wt%). In a deasphalting solvent corresponding to C₅₊Aspect of the deasphalting solvent, said C₅₊The deasphalting solvent may comprise less than 15 wt%, or less than 10 wt%, or less than 5 wt% propane, butane and/or other C₃-C₄Hydrocarbons, or said C₅₊The deasphalting solvent may be substantially free of propane, butane and/or other C₃-C₄Hydrocarbons (less than 1 wt%). In a deasphalting solvent corresponding to C₃₊Aspect of the deasphalting solvent, said C₃₊The deasphalting solvent may comprise less than 10 wt%, or less than 5 wt% of ethane and/or other C₂Hydrocarbons, or said C₃₊The deasphalting solvent may be substantially free of ethane and/or other C₂Hydrocarbons (less than 1 wt%).

Deasphalting of heavy hydrocarbons, such as vacuum residuum, is known in the art and is practiced commercially. The deasphalting process generally corresponds to contacting a heavy hydrocarbon with an alkane solvent (propane, butane, pentane, hexane, heptane, and the like and isomers thereof) in pure form or as a mixture to produce two types of product streams. One type of product stream may be deasphalted oil extracted from the alkanes, which is further separated to produce a deasphalted oil stream. The second type of product stream may be the residual fraction of the feed that is insoluble in the solvent, often referred to as the resid or asphaltene fraction. The deasphalted oil fraction can be further processed to make fuels or lubricating oils. The residual fraction may be further used as a blending component to produce asphalt, fuel oil, and/or other products. The resid fraction can also be used as a feed to gasification processes such as partial oxidation, fluidized bed combustion, or coking processes. The resid can be fed to these processes as a liquid (with or without other components) or a solid (as a particulate or cake).

During solvent deasphalting, the residua boiling-range feed (optionally also including a portion of the vacuum gas oil feed) can be mixed with the solvent. The solvent-soluble portion of the feed is then extracted, leaving a residue that is poorly soluble or insoluble in the solvent. The portion of the deasphalted feedstock extracted with the solvent is often referred to as deasphalted oil. Typical solvent deasphalting conditions include mixing the feed fraction with the solvent in a weight ratio of 1:2 to 1:10, for example 1:8 or less. Typical solvent deasphalting temperatures range from 40 ℃ to 200 ℃, or from 40 ℃ to 150 ℃, depending on the nature of the feed and solvent. The pressure during solvent deasphalting can be from 50psig (345kPag) to 1000psig (-6900 kPag).

It is noted that the above solvent deasphalting conditions represent a general range, and the conditions will vary depending on the feed. For example, under typical deasphalting conditions, increasing the temperature may tend to decrease the yield (or degree of upgrade) of the deasphalted oil produced, while increasing its quality. Under typical deasphalting conditions, increasing the molecular weight of the solvent may tend to increase the yield of deasphalted oil produced while decreasing its quality, since other compounds in the residual fraction may be soluble in the solvent consisting of higher molecular weight hydrocarbons. Under typical deasphalting conditions, increasing the amount of solvent may tend to increase the yield of deasphalted oil produced. As understood by those skilled in the art, the conditions of a particular feed may be selected based on the yield of deasphalted oil resulting from solvent deasphalting. In the use of C₃In the case of deasphalting solvents, the yield from solvent deasphalting may be 40% by weight or less. In some aspects, C is performed₄The deasphalted oil yield may be 50 wt% or less, or 40 wt% or less. In various aspects, with C relative to the weight of deasphalted feed₄₊The deasphalted oil yield for solvent deasphalting can be 50 wt% or greater, or 55 wt% or greater, or 60 wt% or greater, or 65 wt% or greater, or 70 wt% or greater. In aspects in which the feed to be deasphalted includes a vacuum gas oil fraction, the yield from solvent deasphalting may be characterized based on the weight yield of the 950 ° f + (510 ℃) fraction of deasphalted oil relative to the weight of the 510℃ + fraction in the feed. In the use of C₄₊These aspects of the solvent may have a yield of 510 ℃ + deasphalted oil from solvent deasphalting of 40 wt% or more, or 50 wt% or more, or 55 wt% or more, or 60 wt% or more, or 65 wt% or more, or70 wt% or more. In the use of C_4-These aspects of the solvent may yield a 510℃ + deasphalted oil from solvent deasphalting of 50 wt% or less, or 40 wt% or less, or 35 wt% or less, relative to the weight of the 510℃ + fraction in the feed to be deasphalted.

In some aspects, a three-product deasphalting unit can correspond to a system that implements sequential deasphalting to form a deasphalted oil product, a resin product, and a deasphalting unit residue or resid product. In some aspects, sequential deasphalting may involve using different deasphalting solvents in the first and second deasphalting stages, such as using larger hydrocarbons in the first stage (for higher lift deasphalting) and smaller hydrocarbons in the second stage (for lower lift deasphalting). In some aspects, the relative lift between stages during sequential deasphalting may be adjusted at least in part by using different deasphalting temperatures in different stages, with higher temperatures generally corresponding to deasphalting processes with lower lifts.

Deasphalting using three products to form improved product slate

One of the difficulties in processing heavy oil feeds is finding a commercially viable disposal of the total feed. For example, solvent deasphalting can be a useful process for producing higher quality deasphalted oils from the vacuum residuum portion of the feedstock. However, deasphalting also results in the formation of lower quality deasphalting unit residues or resid products. If a reasonably high value disposition cannot be determined for the resid product, it may not be economically feasible to first perform deasphalting. Conversely, if no suitable product disposal is available, the total vacuum residue fraction can be used as a fuel oil blending component rather than attempting to convert a portion of the residue fraction to a higher value product.

One related limitation of heavy oil feed processing is the ability to form a bitumen fraction suitable for further commercial use. Bitumen is useful in a variety of applications such as road and roof tiles. To be suitable for such applications, it may often be desirable for the bitumen product to have one or more characteristics. Part of the difficulty in finding disposal of all portions of the heavy oil feed may be related to the requirement to produce bitumen that meets the target set of characteristics. An example of such a property is the penetration depth (at 25 ℃) of the bitumen. Typical target penetration grades for bitumen at 25 ℃ include 65dmm and 195 dmm. Other properties may include softening point (. degree. C.) and dynamic viscosity (Pa-sec). The formation of a product slate in which the bitumen meets the desired or target set of characteristics can be contrasted with the formation of a product slate in which a substantial portion of the residual oil and/or resin and/or bitumen fraction from deasphalting requires thermal cracking to form the desired product.

Another practical limitation of heavy oil processing can be that the product make-up formed is consistent with the initial feed make-up. The vacuum residue fraction is formed as a bottoms product during the vacuum distillation of the heavy feed. The other fractions formed during the vacuum distillation may correspond to one or more vacuum gas oil fractions, possibly including heavy vacuum gas oil. Such vacuum gas oil fractions represent potentially higher value feeds than vacuum residue fractions. For example, vacuum gas oil fractions are generally suitable without further blending as a feed for lubricating oil and/or fuel production. When deasphalting a vacuum residue fraction, the formation of a desired or target grade of asphalt may require the incorporation of a portion of the vacuum gas oil fraction from the feed makeup to balance the residue product from deasphalting. Thus, the incorporation of vacuum gas oil into lower value products can significantly reduce the effectiveness of the deasphalting process.

In various aspects, using a three-product deasphalting system, while working within the practical limits imposed when attempting to determine product disposal for a full range of feed compositions, it is possible to achieve the production of improved product compositions. For example, using a three-product deasphalting unit can enable the production of higher quality feeds for distillate fuel production while maintaining target asphalt quality and reducing or minimizing the production of lower value byproducts such as fuel oil. Optionally, the volume of product makeup containing products from the three-product deasphalting unit can be compared to the volume of heavy vacuum gas oil and vacuum residue (i.e., bottoms) produced during distillation. In some aspects, the product make up a volume that can correspond to 95 wt% or more, or 98 wt% or more, of the combined volume of the heavy vacuum gas oil and the vacuum residue, based on the blending of the heavy vacuum gas oil and the product from the three-product deasphalting unit. In some aspects, the product make up a volume that can correspond to 105 wt% or less, or 102 wt% or more, of the combined volume of the heavy vacuum gas oil and the vacuum residue, based on the blending of the heavy vacuum gas oil and the product from the three-product deasphalting unit.

For example, table 1 shows modeling calculations for feed and initial deasphalting unit product properties for distillation and deasphalting of the heavy oil fraction in the crude oil slate. The model corresponds to an empirical model based on pilot and commercial scale data. The crudes represented in the model constitute a mixture corresponding to commercially available crude oil sources. In table 1, the "HVGO" and "VTB" rows refer to the amount of heavy vacuum gas oil and vacuum tower bottoms, respectively, produced during the vacuum distillation of the input crude oil constituents. Note that the amounts of "HVGO" and "VTB" in Table 1 were not changed. Table 1 also includes rows for deasphalted oil (DAO), resin and resid yields. These represent the deasphalted products formed from the "VTB" portion of the crude oil. Column shows the use of C₅Solvent, C₄Solvent, or C₃Two-product and three-product deasphalting configurations of the solvent. For a three-product deasphalting configuration, the resin is formed by performing sequential deasphalting, wherein the first stage is substantially the same as the corresponding two-product deasphalting configuration, and the second stage corresponds to a deasphalting process performed on the deasphalted oil from the first stage with the same solvent but at a higher temperature. Thus, for a given solvent type, the amount of DAO varies between the two-product and three-product deasphalting unit configurations, while the resid fraction is the same. The deasphalting unit solvent corresponds to n-pentane (C)₅) N-butane (C)₄) And propane (C)₃)。

TABLE 1 deasphalting unit products

kB/day	C5/2 product	C5/3 product	C4/2 product	C4/3 product	C3/2 product	C3/3 product
							HVGO	9.4	9.4	9.4	9.4	9.4	9.4
VTB	17.0	17.0	17.0	17.0	17.0	17.0
							DAO	14.3	13.0	11.0	9.9	5.7	4.2
Resin composition	0.0	1.3	0.0	1.1	0.0	1.5
							Residual oil	2.7	2.7	6.0	6.0	11.3	11.3

After deasphalting, the heavy vacuum gas oil and deasphalting unit products were blended into commercial products using this model. In this example, a heavy vacuum gas oil and deasphalting unit products are blended to form a) a feed suitable for hydrotreating prior to fluid catalytic cracking to form a distillate fuel product; b) bitumen having a penetration of 65dmm or less at 25 ℃; and c) fuel oil to the extent necessary to handle the full range of deasphalting unit products.

Table 2 shows the blends predicted in the model to form a feed for final catalytic cracking to produce fuel. Table 2 also shows the model predictions of the properties of the resulting blends.

TABLE 2 catalytic cracking feed blends

As shown in table 2, the feed for the final fluid catalytic cracking corresponds to a blend of heavy vacuum gas oil and deasphalted oil. However, both the heavy vacuum gas oil and the deasphalted oil used to form the catalytic cracking feed are less than full. Even though the catalytic cracking feed represents the highest value "product" in the deasphalter/HVGO product slate, a portion of the deasphalted oil and/or heavy vacuum gas oil is still needed to form other products. More generally, the feed for catalytic cracking (for fuel production) or the feed for lube oil production, which is produced by blending products from three-product deasphalting, may have an API gravity of 14 or higher, or 16 or higher. Additionally or alternatively, the conradson carbon content of such a feed may be 10 wt.% or less, or 8.0 wt.% or less, or 6.0 wt.% or less.

Table 2 also shows the product quality characteristics of the catalytic cracking feed. The product qualities shown in table 2 include API gravity and conradson carbon content. As shown in table 2, for the same type of deasphalting solvent, the use of a three-product deasphalting unit achieved the production of a higher quality catalytic cracking feed, but at a lower yield. Higher API gravity (i.e., lower density) and lower conradson carbon content demonstrate higher quality. Further discussion of product quality as part of the complete product make-up will be provided below.

Table 3 shows the blends predicted in the model to form a bitumen with the desired penetration at 25 ℃. Table 3 also shows the predicted product quality of the resulting asphalt blend.

TABLE 3 asphalt blends

In table 3, the rows of resid, resin, DAO, and HVGO represent the amount of each deasphalting unit product fraction (or HVGO fraction) contained in the asphalt blend. The summary indicates the yield of the bitumen product. In table 3, the penetration of all bitumen blends at 25 ℃ was 65 dmm. The asphalt blend of each deasphalting solvent also had approximately the same softening temperature and the same dynamic viscosity at 60 ℃. As shown in table 3, for a given deasphalting solvent, a higher yield of pitch was produced when using a three-product deasphalting unit.

The remaining portion of the deasphalting unit product is then used to form fuel oil. Table 4 shows the fuel oil blends formed so as to simulate the complete deasphalting unit product slate as contained in the commercial product.

TABLE 4 Fuel oil blends

kB/day	C5/2 product	C5/3 product	C4/2 product	C4/3 product	C3/2 product	C3/3 product
							Resin composition	0.0	0.8	0.0	0.9	0.0	1.0
Residual oil	0.0	0.0	2.7	2.3	6.1	6.0
							Small counter	0.0	0.8	2.7	3.2	6.1	7.0

As shown in table 4, for a given deasphalter solvent, the use of three-product deasphalting resulted in an increase in the amount of fuel oil produced.

Taken together, tables 2, 3 and 4 demonstrate the benefits that can be achieved using a three-product deasphalting unit. In particular, the use of a three-product deasphalting unit can be beneficial when it is desired to improve the product quality of a feed for fuel or lubricant production while maintaining a desired asphalt quality and while reducing or minimizing the production of lower value products, such as fuel oil.

To illustrate the benefits, one may derive from using C₅The product of the solvent deasphalting of the two products was used as a baseline. With the two-product deasphalting, if it is desired to improve the quality of the catalytic cracking feed, the degree of deasphalting increase must be reduced. This is switched to use C₄Solvent is used for illustration. In tables 2, 3 and 4, C was used in the deasphalting of the two products₄The solvent can be generated from C₅The second product deasphalted asphalt has asphalt with equivalent quality. The quality of the catalytic cracking feed is also improved. However, the need to dispose of all deasphalting unit products requires the production of a significant portion of fuel oil. In contrast, use of C in a three-product deasphalting unit configuration₅Solvent, a considerable improvement in catalytic cracking feed quality can also be obtained. Comparable bitumen was also produced. Although the yield of catalytic cracking feed was low, the amount of fuel oil produced was also low (0.8 kB/day vs. 2.7 kB/day). Thus, the use of a three-product deasphalting unit providesA process is provided for reducing or minimizing the production of low value fuel oil products while also improving the quality of the catalytic cracking feed. Although more difficult in a direct comparison, when trying to improve the use of the two-product deasphalting unit C₄Similar benefits can be achieved when the solvent produces a catalytically cracked feed.

Hydrotreating and hydrocracking

After deasphalting, the deasphalted product fraction (and any other fractions combined with the deasphalting unit product fraction) may be subjected to further processing, such as further processing to form a lubricating oil base stock, further processing prior to fluid catalytic cracking, and/or further processing for any other suitable purpose. This may include hydrotreating and/or hydrocracking to remove heteroatoms to a desired level, reduce conradson carbon content, and/or provide an increase in Viscosity Index (VI). According to this aspect, the deasphalted oil can be hydroprocessed by demetallization, hydrotreating, hydrocracking, or combinations thereof. Similarly, the resin fraction produced by sequential deasphalting can be hydroprocessed by demetallization, hydrotreating, hydrocracking, or combinations thereof.

The deasphalted oil (or resin fraction) can be hydrotreated and/or hydrocracked with little or no solvent extraction before and/or after deasphalting. As a result, deasphalted oil feeds (or resin fraction based feeds) for hydrotreating and/or hydrocracking can have appreciable aromatic content. In various aspects, the aromatic content of the deasphalted oil feed (or feed based on the resin fraction) can be 50 wt% or more, or 55 wt% or more, or 60 wt% or more, or 65 wt% or more, or 70 wt% or more, or 75 wt% or more, for example up to 90 wt% or more. Additionally or alternatively, the saturated hydrocarbon content of the deasphalted oil feed (or feed based on the resin fraction) may be 50 wt% or less, or 45 wt% or less, or 40 wt% or less, or 35 wt% or less, or 30 wt% or less, or 25 wt% or less, for example as low as 10 wt% or less. In the present discussion and claims, the aromatic content and/or saturated hydrocarbon content of a fraction may be determined based on ASTM D7419.

The reaction conditions of the feed during hydrotreating and/or hydrocracking, including the fractions produced during sequential deasphalting, may be selected to reduce the sulfur content of the feed to a desired level. For example, the resin fraction may contain 1.0 wt.% to 4.0 wt.% sulfur prior to hydrotreating. Hydrotreating can be used to reduce the sulfur content of the resin fraction (or other feed containing products from deasphalting) to 1.0 wt.% or less, or 0.5 wt.% or less, for example to 500wppm, or to 300wppm, or less.

In various aspects, the feed containing the deasphalting unit product fraction can be contacted with the demetallization catalyst prior to contacting the feed with the hydrotreating catalyst. The metal concentration (Ni + V + Fe) of the deasphalted oil can be about 10-100 wppm. Other deasphalting unit products can potentially have higher metal concentrations. Contacting conventional hydrotreating catalysts with feeds having a metals content of 10wppm or higher can result in catalyst deactivation at a rate faster than may be desirable in a commercial environment. Contacting the metal-containing feed with the demetallization catalyst prior to the hydrotreating catalyst can allow at least a portion of the metals to be removed by the demetallization catalyst, which can reduce or minimize deactivation of the hydrotreating catalyst and/or other subsequent catalysts in the process stream. Commercially available demetallization catalysts may be suitable, for example, a large pore amorphous oxide catalyst, which may optionally include group VI and/or group VIII non-noble metals to provide some hydrogenation activity.

In various aspects, a feed containing a deasphalting unit product fraction can contact a hydrotreating catalyst under effective hydrotreating conditions. The catalyst used may include conventional hydroprocessing catalysts, for example comprising at least one non-noble group VIII metal (columns 8-10 of the IUPAC periodic table), preferably Fe, Co and/or Ni, for example Co and/or Ni; and at least one group VI metal (column 6 of the IUPAC periodic Table), preferably Mo and/or W. Such hydroprocessing catalysts optionally comprise a transition metal sulfide impregnated/dispersed on a refractory support or carrier, such as alumina and/or silica. The support or carrier itself typically has no significant/measurable catalytic activity. Catalysts that are substantially free of a support or carrier, commonly referred to as bulk catalysts, generally have a higher volumetric activity than their supported counterparts.

In addition to alumina and/or silica, other suitable support/support materials may include, but are not limited to, zeolites, titania, silica-titania, and titania-alumina suitable aluminas are porous aluminas, such as gamma or η -alumina, having an average pore diameter of 50 to

Or 75 to

Surface area of 100 to 300m²Per g, or from 150 to 250m²(ii)/g; and a pore volume of 0.25 to 1.0cm³In terms of/g, or 0.35 to 0.8cm³(ii) in terms of/g. More generally, for catalysts suitable for hydrotreating distillate (including lube base stock) boiling range feeds in a conventional manner, any convenient size, shape, and/or pore size distribution may be used. Preferably, the support or support material is an amorphous support, such as a refractory oxide. Preferably, the support or carrier material may be free or substantially free of molecular sieve, wherein substantially free of molecular sieve is defined as having a molecular sieve content of less than 0.01 wt.%.

The at least one group VIII non-noble metal in oxide form may generally be present in an amount ranging from 2 to 40 wt.%, preferably from 4 to 15 wt.%. The at least one group VI metal in oxide form may generally be present in an amount ranging from 2 to 70 wt%, preferably from 6 to 40 wt% or from 10 to 30 wt% for the supported catalyst. These weight percentages are based on the total weight of the catalyst. Suitable metal catalysts include cobalt/molybdenum (1-10% Co as an oxide, 10-40% Mo as an oxide), nickel/molybdenum (1-10% Ni as an oxide, 10-40% Co as an oxide), or nickel/tungsten (1-10% Ni as an oxide, 10-40% W as an oxide) on alumina, silica-alumina, or titania.

The hydrotreatment is carried out in the presence of hydrogen. Thus, a hydrogen stream is fed or injected into the vessel or reaction zone or hydroprocessing zone in which the hydroprocessing catalyst is located. The hydrogen contained in the hydrogen "treat gas" is supplied to the reaction zone. The process gas as referred to herein may be pure hydrogen or a hydrogen-containing gas, which is a gas stream containing a sufficient amount of hydrogen for the intended reaction, optionally comprising one or more other gases (e.g. nitrogen and light hydrocarbons such as methane). The process gas stream introduced into the reaction zone will preferably contain at least 50% or more, and more preferably 75% or more, by volume of hydrogen. Optionally, the hydrogen treat gas may be substantially free (less than 1 vol%) of impurities such as H₂S and NH₃And/or such impurities may be substantially removed from the process gas prior to use.

The hydrogen supply rate can be from 100SCF/B (standard cubic feet of hydrogen per barrel feed) (17Nm³/m³) To 10000SCF/B (1700 Nm)³/m³). Preferably at 200SCF/B (34 Nm)³/m³) To 2500SCF/B (420 Nm)³/m³) The range of (1) provides hydrogen. Hydrogen may be supplied to the hydroprocessing reactor and/or reaction zone concurrently with the input feed or separately to the hydroprocessing zone via a separate gas conduit.

Hydrotreating conditions may include a temperature of 200 ℃ to 450 ℃, or 315 ℃ to 425 ℃; a pressure of 250psig (1.8MPag) to 5000psig (34.6MPag) or 300psig (2.1MPag) to 3000psig (20.8 MPag); liquid Hourly Space Velocity (LHSV) of 0.1hr^-1To 10hr^-1(ii) a And a hydrogen treat gas rate of 200scf/B (35.6 m)³/m³) To 10,000scf/B (1781 m)³/m³) Or 500(89 m)³/m³) To 10,000scf/B (1781 m)³/m³)。

In various aspects, a feed containing a deasphalting unit product fraction can be subjected to effective hydrocracking conditionsContacting with a hydrocracking catalyst. Hydrocracking catalysts typically contain sulfided base metals on an acidic support such as amorphous silica alumina, cracking zeolites such as USY, or acidified alumina. These acidic supports are often mixed or combined with other metal oxides such as alumina, titania or silica. Examples of suitable acidic supports include acidic molecular sieves, such as zeolites or silicoaluminophosphates. One example of a suitable zeolite is USY, such as USY zeolite having a pore size of 24.30 angstroms or less. Additionally or alternatively, the catalyst may be a low acidity molecular sieve, for example a USY zeolite having a Si to Al ratio of at least 20, and preferably at least 40 or 50. ZSM-48, e.g. SiO₂With Al₂O₃Non-limiting examples of metals for hydrocracking catalysts include metals or combinations of metals including at least one group VIII metal such as nickel, nickel-cobalt-molybdenum, nickel-tungsten, nickel-molybdenum, and/or nickel-molybdenum-tungsten, additionally or alternatively, hydrocracking catalysts having a noble metal may also be used.

When only one hydrogenation metal is present on the hydrocracking catalyst, the amount of such hydrogenation metal may be 0.1 wt% or more, for example 0.5 wt% or more, or 0.6 wt% or more, based on the total weight of the catalyst. Additionally or alternatively, when only one hydrogenation metal is present, the amount of the hydrogenation metal can be 5.0 wt.% or less, e.g., 3.5 wt.% or less, 2.5 wt.% or less, 1.5 wt.% or less, 1.0 wt.% or less, 0.9 wt.% or less, 0.75 wt.% or less, or 0.6 wt.% or less, based on the total weight of the catalyst. Still additionally or alternatively, when more than one hydrogenation metal is present, the total amount of hydrogenation metal can be 0.1 wt.% or more, such as 0.25 wt.% or more, 0.5 wt.% or more, 0.6 wt.% or more, 0.75 wt.% or more, or 1 wt.% or more, based on the total weight of the catalyst. Still further additionally or alternatively, when more than one hydrogenation metal is present, the total amount of hydrogenation metal can be 35 wt.% or less, for example 30 wt.% or less, 25 wt.% or less, 20 wt.% or less, 15 wt.% or less, 10 wt.% or less, or 5 wt.% or less, based on the total weight of the catalyst. In embodiments where the supported metal comprises a noble metal, the amount of noble metal is typically less than 2.0 wt.%, e.g., less than 1.0 wt.%, 0.9 wt.% or less, 0.75 wt.% or less, or 0.6 wt.% or less. It is noted that hydrocracking under sulfur-containing conditions is typically carried out using base metals as the hydrogenation metal.

Blowing the resin-containing fraction to form bitumen suitable for the application

In some aspects, with C₄₊Deasphalting with a deasphalting solvent can be used to produce deasphalted oil at high levels of lift, for example, 65 wt% or more of deasphalted oil. In such an aspect, sequential deasphalting can be performed to form a resin fraction and a resid fraction. In such an aspect, the resin fraction may correspond to a heavy resin fraction having a viscosity of 5000cSt or more. The heavy resin fraction may be blended with other fractions in an attempt to form a suitable-for-use pitch, or air blowing may be used to further assist in forming a suitable-for-use pitch.

One characteristic of the heavy resin fraction may be a reduced asphaltene content relative to the typical residual oil fraction. Blowing can be an advantageous method to improve the quality of the bitumen fraction containing the heavy resin fraction, based on the reduction of the asphaltene content. It has been found that the degree of improvement in asphaltene-poor crude oil or bitumen by air blowingMay be larger than conventional crude oil fractions. Most crude oils or crude oil fractions exhibit similar behavior when oxidized by blowing. After an initial modest improvement in high temperature properties with little damage to low temperature properties, further aeration of conventional crude oil results in a predictable compromise of high temperature property improvement and low temperature property reduction. Without being bound by any particular theory, it is believed that this compromise in obtaining improved high temperature properties at the expense of less favorable low temperature properties is due to phase instability in the oxidized crude oil or bitumen. Thus, SUPERPAVE according to North American use^TMStandard, air blowing has limited benefit for producing bitumen from conventional crude oil. In contrast, oxidation of asphaltene-lean crude oil by air blowing can be used to improve high temperature properties to a much greater extent with only a modest impact on the corresponding low temperature properties. Thus, aeration may be effectively used to upgrade bitumen-depleted crude oils (including blends containing bitumen-depleted crude oils) that would otherwise be considered unsuitable for making typical north american bitumen grades.

Various types of systems are available for oxidizing crude oil by blowing air. Fig. 1 shows an example of a general asphalt oxidation process. The bitumen feed is passed via line 10 through heat exchanger 1 where it is preheated to a temperature of from 125 ℃ to 300 ℃ and then enters oxidizer vessel 2. Air, first compressed by use of compressor 3 and then passed through knock-out drum 4 to remove any condensed water or other liquid via line 13, is also introduced into oxidizer vessel 2 via line 12. The air flows upwardly through the distributor 15 and counter-currently to the downwardly flowing bitumen. Air is not only a reactant, but also serves to stir and mix the pitch, thereby increasing surface area and reaction rate. As the air rises through the downflowing bitumen, the bitumen consumes oxygen. Steam or water can be sprayed (not shown) into the vapor space above the bitumen to suppress foaming and dilute the oxygen content in the off-gas removed via line 14 and directed to the knockout drum 5 to remove condensed or entrained liquid via line 17. Oxidizer vessel 2 is typically operated at a low pressure of 0 to 2 barg. The temperature of the oxidizer vessel may be from 150 ℃ to 300 ℃, preferably from 200 ℃ to 270 ℃, and more preferably from 250 ℃ to 270 ℃. Preferably the temperature within the oxidizer will be at least 10 c, preferably at least 20 c, and more preferably at least 30 c higher than the incoming bitumen feed temperature. The low pressure tail gas, which contains primarily nitrogen and water vapor, is often directed via line 16 to incinerator 8 where it is combusted and then vented to the atmosphere. The oxidized bitumen product stream is then directed via line 18 and pumped via pump 6 through heat exchanger 1 where it is used to preheat the bitumen feed to be directed to oxidant vessel 2. The hot bitumen product stream is then directed via line 20 to steam generator 7 where it is cooled before it is to be stored.

In an alternative configuration, liquid jet technology may be used to improve the performance of the blowing process. Liquid ejector technology eliminates the need for an air compressor; improved air/oil mixing compared to conventional oxidizer vessels, thereby reducing excess air requirements and reducing the size of the exhaust duct; excess oxygen in the exhaust gas admitted to the fuel gas system is reduced, thereby eliminating the need for an incinerator; and reduces the reaction time, thereby reducing the size requirements of the oxidizer vessel.

The liquid ejector includes the following components: a body having an inlet for the introduction of a motive liquid, a converging nozzle to convert the motive liquid into a high velocity jet, a port on the body for the entrainment of a second liquid or gas (a suction inlet), a diffuser (or venturi), and an outlet where the mixed liquid stream is discharged.

In a liquid ejector, motive liquid at high pressure flows through a converging nozzle into a mixing chamber and forms a high velocity and highly dispersed liquid jet at a distance behind the nozzle, which mixes with entrained gas, accelerates the gas and creates a supersonic liquid-gas flow inside the mixing chamber. The kinetic energy of the liquid jet is transferred to the entrained gas in the mixing chamber, creating a vacuum at the suction inlet. The hypersonic liquid-gas flow enters the throat where it is decelerated by the compression shocks. Thus, the low pressure zone in the mixing chamber is isolated from the high pressure zone located downstream.

FIG. 2 herein is a process flow diagram of a process for oxidizing pitch using a liquid jet. The pitch feed via line 100 is preheated in heat exchanger 60 and combined via line 110 with a portion of the oxidized pitch product from oxidizer vessel 20 and pumped by pump 50 via line 120 to the motive inlet of liquid eductor 30 and mixed with an effective amount of air via knockout drum 70 via line 130 to the suction inlet of liquid eductor 30. Any liquid collected from the separator tank 70 is drained via line 170. The amount of oxidized bitumen product recycled from the oxidiser will be at least 5 times, preferably at least 10 times, and more preferably at least 20 times the volume of the incoming bitumen feed. By an effective amount of air we mean at least a stoichiometric amount, but not so much that it would cause undesirable results from a reaction or process point of view. The stoichiometric amount of air will be determined by the amount of oxidizable component in the particular asphalt feed. It is preferred to use a stoichiometric amount of air.

Any suitable liquid injector may be used as part of the blown gas oxidation process. Liquid ejectors typically comprise a motive inlet, a motive nozzle, a suction inlet, a body, a venturi throat and diffuser, and a discharge interface, wherein hot bitumen at a temperature of 125 ℃ to 300 ℃ is introduced into the motive inlet as a motive liquid, and wherein air is drawn into the suction port and mixed with the bitumen within the ejector body. The air drawn into the suction port of the liquid ejector may be atmospheric air or compressed air. The pressurized air/bitumen mixture is then directed to oxidizer/separation vessel 20 via line 140. The pressure of the mixture exiting the liquid injector will exceed the pressure at which the oxidizer is operating and will be further adjusted to effect introduction of the vent gas generated by the oxidizer into a refinery fuel gas system. The oxidizer vessel 20 operates at a pressure of 0 to 10+ barg, preferably 0 to 5barg and more preferably 0 to 2 barg. The temperature of the oxidant vessel may be from 150 ℃ to 300 ℃, preferably from 200 ℃ to 270 ℃, and more preferably from 250 ℃ to 270 ℃. Preferably the temperature within the oxidizer will be at least 10 c, preferably at least 20 c, and more preferably at least 30 c higher than the incoming bitumen feed temperature. The vent gas is collected overhead via line 150 and passed through knock out drum 70 where the liquid is discharged via line 170 for further processing and the vapor can enter the refinery fuel gas system via line 180 due to its pressure and low oxygen content. The oxidized products are directed through the pump 80, heat exchanger 60, and steam generator 40 via line 190. An effective amount of steam (not shown) may be directed to the vapor space 22 above or below the pitch level 24 in the oxidizer 20 to dilute the oxygen content of the exhaust gas, primarily for safety. An effective amount of steam is at least that amount required to dilute the oxygen content in the generated exhaust gas to a predetermined value. The oxidized product stream then enters product storage via line 190, with a portion thereof being recycled via line 110 to line 120 where it is mixed with fresh feed to serve as the motive fluid necessary for the liquid ejector.

Other embodiments