Integrated enhanced solvent deasphalting and coking system to produce petroleum green coke

Abstract

An integrated system is provided for producing deasphalted oil, high quality petroleum green coke and liquid coker products. An enhanced solvent deasphalting system, is used to treat the feedstock to reduce the level of asphaltenes, N, S and metal contaminants and produce a deasphalted oil with reduced contaminants. A coking system is integrated to produce liquid and gas coking unit products, and petroleum green coke.

Claims

1. An integrated system that is located within the battery limits of a refinery for conversion of a heavy hydrocarbon feedstock containing asphaltenes, sulfur-containing and nitrogen-containing polynuclear aromatic molecules comprising: a mixing vessel in fluid communication with a source of heavy hydrocarbon feedstock, a source of paraffinic solvent, and a source of solid adsorbent material, and having an outlet for discharging a mixture of heavy hydrocarbon feedstock, paraffinic solvent, and adsorbent material; a first separation vessel in fluid communication with the mixing vessel outlet for discharging a mixture, and having an outlet for discharging a liquid phase comprising deasphalted oil and paraffinic solvent and an outlet for discharging a solid phase containing asphaltenes and adsorbent material; a filtration vessel in fluid communication with the first separation vessel outlet for discharging the solid phase and in fluid communication with a source of aromatic or polar solvent stream, and having an outlet for discharging a solvent and asphalt mixture and an outlet for discharging asphalt; a second separation vessel in fluid communication with the first separation vessel outlet for discharging a liquid phase, and having an outlet for discharging paraffinic solvent, and an outlet for discharging deasphalted oil; and a coking unit in fluid communication with the second separation vessel outlet for discharging deasphalted oil, having an outlet for discharging liquid and gas coking products and having an apparatus for removing coke.

2. The integrated system of claim 1, wherein the filtration vessel comprises an outlet in fluid communication with the mixing vessel for discharging adsorbent material.

3. The integrated system of claim 1, wherein the second separation vessel outlet for discharging paraffinic solvent is in fluid communication with the mixing vessel.

4. The integrated system of claim 1, further comprising a fractionator in fluid communication with the filtration vessel outlet for discharging a solvent and asphalt mixture, and having an outlet in fluid communication with the filtration vessel for discharging recycled aromatic or polar solvent and an outlet for discharging asphalt.

5. The integrated system of claim 1, further comprising a coking unit furnace in fluid communication with the second separation vessel outlet for discharging deasphalted oil, and having an outlet in fluid communication with the coking unit for discharging heated deasphalted oil.

6. The integrated system of claim 5, further comprising a coking product fractionator in fluid communication with the outlet of the coking unit for discharging liquid and gas coking products, and having an outlet for discharging a light gas stream, an outlet for discharging a coker naphtha stream, an outlet for discharging light coker gas oil, and an outlet for discharging heavy coker gas oil.

7. The integrated system of claim 6, wherein the coking product fractionator outlet for discharging heavy coker gas oil is in fluid communication with the coking unit furnace.

8. An integrated system that is located within the battery limits of a refinery for conversion of a heavy hydrocarbon feedstock containing asphaltenes, sulfur-containing and nitrogen-containing polynuclear aromatic molecules comprising: a first separation vessel in fluid communication with a source of heavy hydrocarbon feedstock and a solvent inlet for receiving a source of paraffinic solvent, and having an outlet for discharging asphalt stream and an outlet for discharging a mixture of deasphalted oil and paraffinic solvent; a second separation vessel in fluid communication with a source of solid adsorbent material and in fluid communication with the first separation vessel outlet for discharging a mixture, and having an outlet for discharging paraffinic solvent, and an outlet for discharging a mixture of deasphalted oil and adsorbent; a filtration vessel in fluid communication with the second separation vessel outlet for discharging a mixture of deasphalted oil and adsorbent and in fluid communication with a source of an aromatic or polar solvent stream, and having an outlet for discharging adsorbent material and an outlet for discharging a mixture of deasphalted oil and aromatic or polar solvent; a fractionator in fluid communication with the filtration vessel outlet for discharging a mixture of deasphalted oil and aromatic or polar solvent, and having an outlet in fluid communication with the filtration vessel for discharging recycled aromatic or polar solvent, an outlet for discharging deasphalted oil, and an outlet for discharging asphalt; and a coking unit in fluid communication with the fractionator outlet for discharging deasphalted oil, and having an outlet for discharging liquid and gas coking products, and having an apparatus for removing coke.

9. The integrated system of claim 8, wherein the filtration vessel outlet for discharging adsorbent material is in fluid communication with the second separation vessel.

10. The integrated system of claim 8, wherein the second separation vessel outlet for discharging paraffinic solvent is in fluid communication with the mixing vessel.

11. The integrated system of claim 8, further comprising a coking unit furnace in fluid communication with the fractionator outlet discharging deasphalted oil, and having an outlet in fluid communication with the coking unit for discharging heated deasphalted oil.

12. The integrated system of claim 11, further comprising a coking product fractionator in fluid communication with the outlet of the coking unit for discharging liquid and gas coking products, and having an outlet for discharging a light gas stream, an outlet for discharging a coker naphtha stream, an outlet for discharging light coker gas oil, and an outlet for discharging heavy coker gas oil.

13. The integrated system of claim 12, wherein the coking product fractionator outlet for discharging heavy coker gas oil is in fluid communication with the coking unit furnace.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The invention will be described in further detail below and with reference to the attached drawings in which the same or similar elements are referred to by the same number, and where:

(2) FIG. 1 is a process flow diagram of one embodiment of an integrated enhanced solvent deasphalting and coking process; and

(3) FIG. 2 is a process flow diagram of a second embodiment of an integrated enhanced solvent deasphalting and coking process.

DETAILED DESCRIPTION OF THE INVENTION

(4) The process and system herein facilitates production of coker liquid and gas fractions and petroleum green coke from heavy crude oils or fractions having asphaltenes, metal and sulfur content that typically has lower market value compared to light crude oils or fractions. Enhanced solvent deasphalting processes, such as those described in commonly owned U.S. Pat. No. 7,566,394, which is incorporated by reference herein in its entirety, are used to process the heavy crude oils or fractions. The deasphalted oil is thermally cracked in a coking unit, such as a delayed coking unit. In contrast to typical coking operations in which the coke is low market value by-product, in the integrated process herein, using as an initial feed heavy crude oils or fractions having reduced asphaltenes, metal and sulfur content, petroleum green coke recovered from the coker unit drums is low in sulfur and metals. The recovered petroleum green coke can be used as high quality, low sulfur and metal content fuel grade (shot) coke, and/or a raw material for production of marketable grades of coke including anode grade coke (sponge) and/or electrode grade coke (needle).

(5) The deasphalted oil is thermally cracked in a coking unit, such as a delayed coking unit. In contrast to typical coking operations in which the coke is low market value by-product, in the integrated process herein, high quality petroleum green coke recovered from the coker unit drums is low in sulfur and metals. The recovered high quality petroleum green coke can be used as high quality, low sulfur and metal content fuel grade (shot) coke, and/or a raw material for production of low sulfur and metal content marketable grades of coke including anode grade coke (sponge) and/or electrode grade coke (needle). Table 1 shows the properties of these types of coke. In accordance with certain embodiments of the process herein, calcination of the petroleum green coke recovered from the coking drums produces sponge and/or needle grade coke, for instance, suitable for use in the aluminum and steel industries. Calcination occurs by thermal treatment to remove moisture and reduce the volatile combustible matter.

(6) TABLE-US-00001 TABLE 1 Calcined Calcined Fuel Sponge Needle Property Units Coke Coke Coke Bulk Density Kg/m.sup.3 880 720-800 670-720 Sulfur W % (max) 3.5-7.5 1.0-3.5 0.2-0.5 Nitrogen ppmw (max) 6,000 — 50 Nickel ppmw (max) 500 200 7 Vanadium ppmw 150 350 — Volatile W % (max) 12 0.5 0.5 Combustible Material Ash Content W % (max) 0.35 0.40 0.1 Moisture Content W % (max)  8-12 0.3 0.1 Hardgrove W % 35-70  60-100 — Grindability Index (HGI) Coefficient of ° C. — — 1-5 thermal expansion, E + 7

(7) As used herein, “high quality petroleum green coke” refers to petroleum green coke recovered from a coker unit that when calcined, possesses the properties as in Table 1, and in certain embodiments possessing the properties in Table 5 concerning calcined sponge coke or calcined needle coke identified in Table 1.

(8) As used herein, a process that operates “within the battery limits of a refinery” refers to a process that operates with a battery of unit operations along with their related utilities and services, distinguished from a process whereby effluent from a unit operation is collected, stored and/or transported to a separate unit operations or battery of unit operations.

(9) In one embodiment, of a process herein, which can be carried out within the battery limits of a refinery and on a continuous or semi-continuous basis, a heavy hydrocarbon feedstock is subjected to enhanced solvent deasphalting in the presence of an effective quantity of solid adsorbent material to adsorb sulfur-containing compounds or nitrogen-containing polynuclear aromatic molecules concurrently with solvent assisted removal of asphaltenes. Contaminants are adsorbed and the solvent and deasphalted oil fraction is removed as a separate stream from which the solvent is recovered for recycling. The adsorbent having contaminants adsorbed thereon and the asphalt bottoms are mixed with aromatic and/or polar solvents to desorb the contaminants and washed as necessary to clean the adsorbent, which can preferably be recovered and recycled. The solvent-asphalt mixture is sent to a fractionator for recovery and recycling of the aromatic or polar solvent. Bottoms from the fractionator include the desorbed contaminants are further processed as appropriate. The deasphalted oil having reduced contaminants is thermally cracked in a coking unit, such as a delayed coking unit, and coker liquid and gas products are recovered, along with high quality petroleum green coke.

(10) In another embodiment, a heavy hydrocarbon feedstock is subjected to a first separation step in a solvent deasphalting process to produce a primary deasphalted oil phase and discharge a primary asphalt phase. An effective quantity of solid adsorbent material mixed with the primary deasphalted oil phase, which contains the deasphalted oil and paraffinic solvent. Sulfur-containing and/or nitrogen-containing polynuclear aromatic molecules in the deasphalted oil are adsorbed by the solid adsorbent material. The paraffinic solvent is separated from the deasphalted oil and adsorbent material, and the solvent is recovered for recycling. A slurry containing the adsorbent having contaminants adsorbed thereon and deasphalted oil is mixed with aromatic and/or polar solvents to desorb the contaminants, and washed as necessary to clean the adsorbent, which can preferably be recovered and recycled. The deasphalted oil mixture is sent to a fractionator for recovery and recycling of the aromatic and/or polar solvents. The deasphalted oil having reduced contaminants is thermally cracked in a coking unit, such as a delayed coking unit, and coker liquid and gas products are recovered, along with high quality petroleum green coke.

(11) The solid adsorbent material can be selected from the group consisting of clay (for instance, attapulgus clay), silica, alumina, silica-alumina, titania-silica, activated carbon, molecular sieves, fresh zeolitic catalyst materials, used zeolitic catalyst materials, and combinations comprising one or more of the foregoing. The material is provided in particulate form of suitable dimension, such as granules, extrudates, tablets, spheres, or pellets of a size in the range of 4-60 mesh. The quantity of the solid adsorbent material used in the embodiments herein is about 0.1:1 to 20:1 W/W, and preferably about 1:1 to 10:1 W/W (feed-to-adsorbent).

(12) In the herein embodiments, the coking unit is integrated with an enhanced solvent deasphalting process to produce coker liquid and gas products and recover high quality petroleum green coke suitable for production of marketable coke from the starting heavy hydrocarbon feedstock. Advantageously, the integrated processes herein facilitate recovery of such high quality petroleum green coke since the feed to the delayed coking unit has desirable qualities. In particular, the deasphalted oil stream in the present process is characterized by a sulfur content of generally less than about 3.5 wt %, in certain embodiments less than about 2.5 wt % and in further embodiments less than about 1 wt %, and a metals content of less than about 700 ppmw, in certain embodiments less than about 400 ppmw and in further embodiments less than about 100 ppmw. Use of this feedstream results in a high quality petroleum coke product that can be used as raw material to produce low sulfur marketable grades of coke including anode grade coke (sponge) and/or electrode grade coke (needle), in an efficient integrated process.

(13) Coking is a carbon rejection process in which low-value atmospheric or vacuum distillation bottoms are converted to lighter products which in turn can be hydrotreated to produce transportation fuels, such as gasoline and diesel. Conventionally, coking of residuum from heavy high sulfur, or sour, crude oils is carried out primarily as a means of utilizing such low value hydrocarbon streams by converting part of the material to more valuable liquid and gas products. Typical coking processes include delayed coking and fluid coking.

(14) In the delayed coking process, feedstock is typically introduced into a lower portion of a coking feed fractionator where one or more lighter materials are recovered as one or more top fractions, and bottoms are passed to a coking furnace. In the furnace bottoms from the fractionator and optionally heavy recycle material are mixed and rapidly heated in a coking furnace to a coking temperature, for instance, in the range of 480° C. to 530° C., and then fed to a coking drum. The hot mixed fresh and recycle feedstream is maintained in the coke drum at coking conditions of temperature and pressure where the feed decomposes or cracks to form coke and volatile components.

(15) Table 2 provides delayed coker operating conditions for production of certain grades of petroleum green coke in the process herein:

(16) TABLE-US-00002 TABLE 2 Variable Unit Fuel Coke Sponge Coke Needle Coke Temperature ° C. 488-500 496-510 496-510 Pressure Kg/cm.sup.2 1 1.2-4.1 3.4-6.2 Recycle Ratio % 0-5  0-50  60-120 Coking time hours  9-18 24 36

(17) The volatile components are recovered as vapor and transferred to a coking product fractionator. One or more heavy fractions of the coke drum vapors can be condensed, for instance quenching or heat exchange. In certain embodiments the contact the coke drum vapors are contacted with heavy gas oil in the coking unit product fractionator, and heavy fractions form all or part of a recycle oil stream having condensed coking unit product vapors and heavy gas oil. In certain embodiments, heavy gas oil from the coking feed fractionator is added to the flash zone of the fractionator to condense the heaviest components from the coking unit product vapors.

(18) Coking units are typically configured with two parallel drums and operated in a swing mode. When the coke drum is full of coke, the feed is switched to another drum, and the full drum is cooled. Liquid and gas streams from the coke drum are passed to a coking product fractionator for recovery. Any hydrocarbon vapors remaining in the coke drum are removed by steam injection. The coke remaining in the drum is typically cooled with water and then removed from the coke drum by conventional methods, for instance, using hydraulic and/or mechanical techniques to remove green coke from the drum walls for recovery.

(19) Recovered petroleum green coke is suitable for production of marketable coke, and in particular anode (sponge) grade coke effective for use in the aluminum industry, or electrode (needle) grade coke effective for use in the steel industry. In the delayed coking production of high quality petroleum green coke, unconverted pitch and volatile combustible matter content of the green coke intermediate product subjected to calcination should be no more than about 15 percent by weight, and preferably in the range of 6 to 12 percent by weight.

(20) In certain embodiments, one or more catalysts and additives can be added to the fresh feed and/or the fresh and recycle oil mixture prior to heating the feedstream in the coking unit furnace. The catalyst can promote cracking of the heavy hydrocarbon compounds and promote formation of the more valuable liquids that can be subjected to hydrotreating processes downstream to form transportation fuels. The catalyst and any additive(s) remain in the coking unit drum with the coke if they are solids, or are present on a solid carrier. If the catalyst(s) and/or additive(s) are soluble in the oil, they are carried with the vapors and remain in the liquid products. Note that in the production of high quality petroleum green coke, catalyst(s) and/or additive(s) which are soluble in the oil can be favored in certain embodiments to minimize contamination of the coke.

(21) The feed to the embodiments of the enhanced solvent deasphalting systems herein can be a heavy hydrocarbon stream such as crude oils, bitumens, heavy oils, shale oils and refinery streams that include atmospheric and vacuum residues, fluid catalytic cracking slurry oils, coker bottoms, visbreaking bottoms and coal liquefaction by-products and mixtures thereof having asphaltenes, sulfur, nitrogen and polynuclear aromatic molecules, for instance, that typically reduce the market value of the material compared to similar streams having lesser quantities of these constituents.

(22) For the purpose of this simplified schematic illustrations and description, the numerous valves, pumps, temperature sensors, electronic controllers and the like that are customarily employed in refinery operations and that are well known to those of ordinary skill in the art are not shown.

(23) Referring to FIG. 1, an embodiment of an integrated enhanced solvent deasphalting and coking process and system is shown, includes a mixing vessel 10, a first separation vessel 20, a filtration vessel 30, a fractionator 40, a second separation vessel 50, a coking unit furnace 60, delayed coking drums 70a and 70b, and a coking product fractionator 80.

(24) In a process for producing high quality petroleum green coke and coker liquid and gas products operation of a system according to FIG. 1, a heavy hydrocarbon feedstream 2, a paraffinic solvent 4 and solid adsorbent slurry 6 having an effective quantity of solid adsorbent material are introduced into the mixing vessel 10. Mixing vessel 10 is equipped with suitable mixing means, for instance, rotary stirring blades or paddles, which provide a gentle, but thorough mixing of the contents.

(25) The rate of agitation for a given vessel and mixture of adsorbent, solvent and feedstock is selected so that there is minimal, if any, attrition of the adsorbent granules or particles. The mixing is continued for 30 to 150 minutes, the duration being related to the components of the mixture.

(26) The mixture of heavy oil 2, paraffinic solvent 4 and solid adsorbent 6 is discharged through line 12 to a first separation vessel 20 at a temperature and pressure that is below the critical temperature and pressure of the solvent to separate the feed mixture into an upper layer comprising light and less polar fractions that are removed as stream 22 and bottoms comprising asphaltenes and the solid adsorbent 24. A vertical flash drum can be utilized for this separation step.

(27) Conditions in the mixing vessel and first separation vessel are maintained below the critical temperature and pressure of the solvent. In certain embodiments the solvent selected for use in the mixing vessel and first separation vessel in the enhanced solvent deasphalting process herein is a C.sub.3 to C.sub.7 paraffinic solvent. The following Table 3 provides critical temperature and pressure data for C.sub.3 to C.sub.7 paraffinic solvents:

(28) TABLE-US-00003 TABLE 3 Carbon Number Temperature, ° C Pressure, bar C.sub.3 97 42.5 C.sub.4 152 38.0 C.sub.5 197 34.0 C.sub.6 235 30.0 C.sub.7 267 27.5

(29) The asphalt and adsorbent slurry 24 is mixed with an aromatic and/or polar solvent stream 26 in a filtration vessel 30 to separate and clean the adsorbent material. The solvent stream 26 can include benzene, toluene, xylenes, tetrahydrofuran, methylene chloride. Solvents can be selected based on their Hildebrand solubility factors or on the basis of two-dimensional solubility factors. The overall Hildebrand solubility parameter is a well-known measure of polarity and has been tabulated for numerous compounds. (See, for example, Journal of Paint Technology, Vol. 39, No. 505, February 1967). The solvents can also be described by two-dimensional solubility parameters, that is, the complexing solubility parameter and the field force solubility parameter. (See, for example, I. A. Wiehe, Ind. & Eng. Res., 34(1995), 661). The complexing solubility parameter component which describes the hydrogen bonding and electron donor-acceptor interactions measures the interaction energy that requires a specific orientation between an atom of one molecule and a second atom of a different molecule. The field force solubility parameter which describes van der Waal's and dipole interactions measures the interaction energy of the liquid that is not impacted by changes in the orientation of the molecules.

(30) In certain embodiments the polar solvent, or solvents, if more than one is employed, used in filtration vessel 30 has an overall solubility parameter greater than about 8.5 or a complexing solubility parameter of greater than one and a field force parameter value greater than 8. Examples of polar solvents meeting the desired solubility parameter are toluene (8.91), benzene (9.15), xylene (8.85), and tetrahydrofuran (9.52). Preferred polar solvents for use in the practice of the invention are toluene and tetrahydrofuran.

(31) In certain embodiments, the adsorbent slurry and asphalt mixture 24 is washed with two or more aliquots of the aromatic or polar solvent 26 in the filtration vessel 30 in order to dissolve and remove the adsorbed compounds. The clean solid adsorbent stream 38, is recovered and recycled to the mixing vessel 10, an asphalt stream 36 is recovered, and spent adsorbent is discharged 34. A solvent-asphalt mixture 32 is withdrawn from the filtering vessel 30 and sent to a fractionator 40 to separate the solvent from the asphalt containing heavy polynuclear aromatic compounds which are withdrawn as stream 42 for appropriate disposal. The clean aromatic and/or polar solvent is recovered as stream 44 and recycled to filtration vessel 30.

(32) The recovered deasphalted oil and solvent stream from the first separation vessel 22 is introduced into a second separation vessel 50 maintained at an effective temperature and pressure to separate solvent from the deasphalted oil, such as between the solvent's boiling and critical temperature, under a pressure of between one and three bars. The solvent stream 52 is recovered and returned to the mixing vessel 10, in certain embodiments in a continuous operation. The deasphalted oil stream 54 is discharged from the bottom of the vessel 50.

(33) In one example, analyses for sulfur using ASTM D5453, nitrogen using ASTM D5291, and metals (nickel and vanadium) using ASTM D3605 indicate that the oil has a greatly reduced level of contaminants, that is, it contains no metals, and about 80 W % of the nitrogen and 20-50 W % of the sulfur which were present in the original feedstream have been removed.

(34) A portion 55 (for instance, 10-100%) of the discharged deasphalted oil stream 54 is processed a coking operation to produce coker gas and liquid products and high quality petroleum green coke. In certain embodiments, as shown in FIG. 1, a delayed coking operation is used. The discharged deasphalted oil stream 55 is charged to a delayed coking furnace 60 where the contents are rapidly heated to an effective coking temperature, such as the range of about 480° C. to 530° C., and then fed to delayed coking drum 70a or 70b. In certain embodiments, two or more parallel coking drums 70a and 70b are provided and are operated in swing mode, such that when one of the drums is filled with coke, the deasphalted oil stream is transferred to the empty parallel drum and coke, in certain embodiments anode grade coke, is recovered from the filled drum 74. A liquid and gas delayed coker product stream 72 is recovered from the coker drum 70a or 70b. Any hydrocarbon vapors remaining in the coke drum can be removed by steam injection.

(35) The liquid and gas delayed coker product stream 72 is introduced into a coking product stream fractionator where it is fractionated to yield separate product streams that can include a light gas stream 82, a coker naphtha stream 84, a light coker gas oil stream 86 and a heavy coker gas oil stream 88. Optionally, all or a portion of the heavy coker gas oil stream 88 is recycled to the coking unit furnace 60.

(36) The coke remaining in coker drum 70a or 70b is cooled, for instance, water quenched, and removed from the coke drum as recovered coke product 74. The coke can be removed by mechanical or hydraulic operations. For instance, coke can be cut from the coke drum with a high pressure water nozzle. According to the process herein, the recovered coke is high quality petroleum green coke.

(37) Advantageously, the integrated process facilitates production of high quality petroleum green coke from the coking operation since the intermediate feed thereto, the deasphalted/desulfurized oil stream, has desirable qualities, that is, low content of asphaltenes and sulfur-containing and nitrogen-containing polynuclear aromatics.

(38) FIG. 2 depicts another embodiment of an integrated enhanced solvent deasphalting and coking process and system. The system includes a first separation vessel 120, a second separation vessel 150, a filtration vessel 130, a fractionator 140, a coking unit furnace 160, delayed coking drums 170a and 170b, and a coking product fractionator 180.

(39) In a process for producing high quality petroleum green coke and coker liquid and gas products operation of a system according to FIG. 2, a heavy hydrocarbon feedstream 102 and a paraffinic solvent 104 are introduced into a first separation zone 120 in which asphalt is separated from the feedstream and discharged from the first separation zone 120 as stream 124. Conditions in the first separation vessel are maintained below the critical temperature and pressure of the solvent. In certain embodiments the solvent selected for use in the first separation vessel in the enhanced solvent deasphalting process herein is a C.sub.3 to C.sub.7 paraffinic solvent.

(40) A combined deasphalted oil and solvent stream 122 is discharged from the first separation zone 120 and mixed with an effective quantity of solid adsorbent material 106.

(41) The deasphalted oil, solvent, and solid adsorbent mixture is passed to the second separation zone 150 where the mixture is maintained at an effective temperature and pressure to separate solvent from the deasphalted oil, such as between the solvent's boiling and critical temperature, under a pressure of between one and three bars. In addition, the mixture is maintained in the second separation zone 150 for a time sufficient to adsorb on the adsorbent material any remaining asphaltenes and/or sulfur-containing polynuclear aromatic molecules and/or nitrogen-containing polynuclear aromatic molecules. The solvent is then separated and recovered from the deasphalted oil and adsorbent material and recycled as stream 152 to the first separation zone 120.

(42) A slurry 155 of deasphalted oil and adsorbent from the second separation vessel 150 is mixed with an aromatic and/or polar solvent stream 126 in a filtration vessel 130 to separate and clean the adsorbent material. The solvent stream 126 can include benzene, toluene, xylenes, tetrahydrofuran, methylene chloride. Solvents can be selected based on their Hildebrand solubility factors or on the basis of two-dimensional solubility factors as discussed above.

(43) In certain embodiments, the deasphalted oil and adsorbent mixture 155 is preferably washed with two or more aliquots of aromatic or polar solvent 126 in the filtration vessel 130 in order to dissolve and remove the adsorbed sulfur-containing and nitrogen-containing compounds. The clean solid adsorbent stream 138, is recovered and recycled for mixing with the deasphalted oil stream 122. Spent adsorbent material is discharged from the filtration vessel as stream 134. The deasphalted oil and solvent mixture 132 is passed from the filtration vessel 130 to the fractionator 140 to separate the solvent from the asphalt containing heavy polynuclear aromatic compounds which are withdrawn as stream 142 for appropriate disposal. The clean aromatic and/or polar solvent is recovered as stream 144 and recycled to filtration vessel 130.

(44) A portion 193 (for instance, 10-100%) discharged deasphalted oil stream 192 is processed a coking operation to produce coker gas and liquid products and high quality petroleum green coke. In certain embodiments, as shown in FIG. 2, a delayed coking operation is used. The discharged deasphalted oil stream 193 is charged to a delayed coking furnace 160 where the contents are rapidly heated to an effective coking temperature, such as the range of about 480° C. to 530° C., and then fed to delayed coking drum 170a or 170b. In certain embodiments, two or more parallel coking drums 170a and 170b are provided and are operated in swing mode, such that when one of the drums is filled with coke, the deasphalted oil stream is transferred to the empty parallel drum and coke is recovered from the filled drum 174. A liquid and gas delayed coker product stream 172 is recovered from the coker drum 170a or 170b. Any hydrocarbon vapors remaining in the coke drum can be removed by steam injection.

(45) The liquid and gas delayed coker product stream 172 is introduced into a coking product stream fractionator where it is fractionated to yield separate product streams that can include a light gas stream 182, a coker naphtha stream 184, a light coker gas oil stream 186 and a heavy coker gas oil stream 188. Optionally, all or a portion of the heavy coker gas oil stream 188 is recycled to the coking unit furnace 160.

(46) The coke remaining in coker drum 170a or 170b is cooled, for instance, water quenched, and removed from the coke drum as recovered coke product 174. The coke can be removed by mechanical or hydraulic operations. According to the process herein, the recovered coke is high quality petroleum green coke.

(47) By integrating an enhanced solvent deasphalting process with a delayed coking process, the deasphalted oil feedstream to the coking unit does not contain sulfur-containing and nitrogen-containing polynuclear aromatic molecules, thereby resulting in the production of high quality petroleum green coke. Moreover, by recycling both solvents as well as the solid adsorbent material, economic and environmental advantages are achieved. In certain embodiments, when activated carbon is used as an adsorbent in the solvent deasphalting unit before or after the desorption step, it can be used as fuel, for instance, in associated power plants.

(48) Computer models can be used advantageously in evaluating whether process modifications are technically feasible and economically justifiable. The use of computer modeling is described by J. F. Schabron and J. G. Speight in an article entitled “An Evaluation of the Delayed-Coking Product Yield of Heavy Feedstocks Using Asphaltenes Content and Carbon Residue”, Oil & Gas Science and Technology—Rev. IFP, Vol. 52 (1997), No. 1, pp. 73-85. A coking process model commonly used in the industry was modified to reflect the presence of light components and the corresponding yields based on the mid-boiling temperatures of the respective cuts. The model also included experimental data regarding the characteristics of the feedstream. Three types of residual oils were delayed coked at the same conditions to see the impact of feedstock quality on the product yields and coke quality. The properties of the feedstocks are summarized in Table 4. The feedstream are subjected to delayed coking at a temperature of 496° C. from the furnace outlet and at atmospheric pressure.

(49) TABLE-US-00004 TABLE 4 Arab Heavy Property Vacuum Residue DOA-SDA DAO-ESDA API Gravity, ° 9 14.16 14.5 SG 1.007 0.971 0.969 Sulfur, W % 4.38 3.31 2.9 Nitrogen, W % 0.4833 0.0835 0.017 CCR, W % 24.3 7.32 4.1 Nickel, ppmw 59 2 0.1 Vanadium, ppmw 182 8 0.1

(50) DAO-SDA: Solvent deasphalted oil using conventional solvent deasphalting technology

(51) DAO-ESDA: Solvent deasphalted oil using enhanced solvent deasphalting technology (with adsorbents)

(52) The Arab heavy residue is the heaviest and dirties of the oil tested and DAO-ESDA is the cleanest oil tested. The product yields from the delayed coking operations are shown in Table 5.

(53) TABLE-US-00005 TABLE 5 Arab Heavy Yields, W % Vacuum Residue DOA-SDA DAO-ESDA Coke 38.9 11.7 6.6 Gas 11.3 8.9 8.4 Naphtha 19.6 13.8 12.7 Light Coker Gas Oil 17.3 36.9 37.8 Heavy Coker Gas Oil 12.9 28.7 34.6 Total 100.0 100.0 100.0

(54) Arab heavy vacuum residue yielded the highest amount of coke (38.9 W %) and a substantial drop 70 W % is observed when the vacuum residue is deasphalted. When the vacuum residue is solvent deasphalted with adsorbents, and the deasphalteed the coke yield decreased further by 83 W % to 6.6 W %.

(55) The sulfur and metals levels are also calculated for the three feedstock and summarized in Table 6.

(56) TABLE-US-00006 TABLE 6 Arab Heavy DOA- DAO- Vacuum Residue SDA ESDA *Specification Sulfur, W % 7.5 4.5 3.2 1-3.5 Metals, ppmw 620 85 3 550 *Anode grade coke

(57) As seen the deasphalted oil obtained from enhanced solvent deasphalting unit, which utilizes adsorbent, produces high coke meeting the anode grade coke specification.

(58) Petroleum green coke recovered from a delayed coker unit is subjected to calcination. In particular, samples of about 3 kg of Petroleum green coke were calcined according to the following heat-up program: Room Temperature to 200° C. at 200° C./h heating rate; 200° C. to 800° C. at 30° C./h heating rate; 800° C. to 1100° C. at 50° C./h heating rate; Soaking Time at 1,100° C.: 20 h.

(59) Table 7 shows the properties of the samples of petroleum green coke and Table 8 shows the properties of the calcium samples.

(60) TABLE-US-00007 TABLE 7 Sam- Sam- Property Method Unit Range ple 1 ple 2 Water Content ISO 11412 % 6.0-15.0 0.0 0.0 Volatile Matter ISO 9406 % 8.0-12.0 4.8 5.9 Hardgrove ISO 5074 — 60-100 41 50 Grindability Index XRF Analysis ISO 12980 %/ppm 0.50-4.00  3.40 3.36 S V Ni Si Fe Al Na Ca 50-350 83 76 P 50-220 80 77 K Mg 20-250 71 45 Pb 50-400 92 154 50-250 71 45 20-120 44 27 20-120 18 13 1-20 2 1 5-15 0 0 10-30  13 11 1-5  0 0 Ash Content ISO 8005 % 0.10-0.30  0.08 0.08

(61) TABLE-US-00008 TABLE 8 Property Method Unit Range Sample 1 Sample 2 Water Content ISO 11412 % 0.0-0.2 0.0 0.0 Volatile Matter ISO 9406 % 0.0-0.5 0.3 0.5 Hardgrove ISO 5074 — — 41 49 Grindability Index Ash Content ISO 8005 % 0.10-0.30 0.04 0.07

(62) The method and system of the present invention have been described above and in the attached drawings; however, modifications will be apparent to those of ordinary skill in the art and the scope of protection for the invention is to be defined by the claims that follow.