Patent Publication Number: US-11021663-B2

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

Description:
RELATED APPLICATIONS 
     This application is a continuation application of U.S. patent application Ser. No. 16/001,445 filed on Jun. 6, 2018, which is a divisional application of U.S. patent application Ser. No. 15/220,896 filed on Jul. 27, 2016, which claims the benefit of priority of U.S. Provisional Patent Application No. 62/197,342 filed Jul. 27, 2015, which are all incorporated by reference herein. 
    
    
     BACKGROUND OF THE INVENTION 
     Field of the Invention 
     The invention relates to integrated enhanced solvent deasphalting and delayed coking processes for production of liquid and gas coking unit products, high quality petroleum green coke, and asphalt. 
     Description of Related Art 
     Crude oils contain heteroatomic molecules, including polyaromatic molecules, with heteroatomic constituents such as sulfur, nitrogen, nickel, vanadium and others in quantities that can adversely affect the refinery processing of the crude oil fractions. Light crude oils or condensates have sulfur concentrations as low as 0.01 percent by weight (W %). In contrast, heavy crude oils and heavy petroleum fractions have sulfur concentrations as high as 5-6 W %. Similarly, the nitrogen content of crude oils can be in the range of 0.001-1.0 W %. These impurities must be removed during refining to meet established environmental regulations for the final products (for instance, gasoline, diesel, fuel oil), or for the intermediate refining streams that are to be processed for further upgrading, such as isomerization reforming. Contaminants such as nitrogen, sulfur and heavy metals are known to deactivate or poison catalysts. 
     In a typical refinery, crude oil is first fractionated in the atmospheric distillation column to separate sour gas including methane, ethane, propane, butanes and hydrogen sulfide, naphtha (36-180° C.), kerosene (180-240° C.), gas oil (240-370° C.) and atmospheric residue, which are the hydrocarbon fractions boiling above 370° C. The atmospheric residue from the atmospheric distillation column is either used as fuel oil or sent to a vacuum distillation unit, depending upon the configuration of the refinery. Principal products from the vacuum distillation are vacuum gas oil, comprising hydrocarbons boiling in the range 370-520° C., and vacuum residue, comprising hydrocarbons boiling above 520° C. 
     Naphtha, kerosene and gas oil streams derived from crude oils or other natural sources, such as shale oils, bitumens and tar sands, are treated to remove the contaminants, such as sulfur, that exceed the specification set for the end product(s). Hydrotreating of these individual fractions is the most common refining technology used to remove these contaminants. Vacuum gas oil is processed in a hydrocracking unit to produce naphtha and diesel, or in a fluid catalytic cracking (FCC) unit to produce mainly gasoline, light cycle oil (LCO) and heavy cycle oil (HCO) as by-products, the former being used as a blending component in either the diesel pool or in fuel oil, the latter being sent directly to the fuel oil pool. 
     Heavier fractions from the atmospheric and vacuum distillation units can contain asphaltenes. Asphaltenes are solid in nature and comprise polynuclear aromatics, smaller aromatics and resin molecules. The chemical structures of asphaltenes are complex and include polynuclear hydrocarbons having molecular weights up to 20,000 joined by alkyl chains. Asphaltenes also include nitrogen, sulfur, oxygen and metals such as nickel and vanadium. They are present in crude oils and heavy fractions in varying quantities. Asphaltenes exist in small quantities in light crude oils, or not at all in all condensates or lighter fractions. However, they are present in relatively large quantities in heavy crude oils and petroleum fractions. Asphaltenes have been defined as the component of a heavy crude oil fraction that is precipitated by addition of a low-boiling paraffin solvent, or paraffin naphtha, such as normal pentane, and is soluble in carbon disulfide and benzene. In certain methods their concentrations are defined as the amount of asphaltenes precipitated by addition of an n-paraffin solvent to the feedstock, for instance, as prescribed in the Institute of Petroleum Method IP-143. The heavy fraction can contain asphaltenes when it is derived from carbonaceous sources such as petroleum, coal or oil shale. There is a close relationship between asphaltenes, resins and high molecular weight polycyclic hydrocarbons. Asphaltenes are hypothesized to be formed by the oxidation of natural resins. The hydrogenation of asphaltic compounds containing resins and asphaltenes produces heavy hydrocarbon oils, that is, resins and asphaltenes are hydrogenated into polycyclic aromatic or hydroaromatic hydrocarbons. They differ from polycyclic aromatic hydrocarbons by the presence of oxygen and sulfur in varied amounts. 
     Upon heating above about 300-400° C., asphaltenes generally do not melt but rather decompose, forming carbon and volatile products. They react with sulfuric acid to form sulfonic acids, as might be expected on the basis of the polyaromatic structure of these components. Flocs and aggregates of asphaltenes will result from the addition of non-polar solvents, for instance, paraffinic solvents, to crude oil and other heavy hydrocarbon oil feedstocks. 
     Therefore, it is clear that significant measures must be taken during processing of crude oils and heavy fractions to deal with asphaltenes. Failure to do so interferes with subsequent refining operations. 
     There are several processing options for the heavy fractions such as vacuum residue, including hydroprocessing, coking, visbreaking, gasification and solvent deasphalting. In the solvent deasphalting process, the asphalt fraction, for instance, having 6-8 W % hydrogen, is separated from the vacuum residue by contact with a paraffinic solvent (for instance, C 3 -C 7 ) at or below the solvents&#39; critical temperatures and pressures. The deasphalted oil, for instance, having 9-11 W % hydrogen, is characterized as a heavy hydrocarbon fraction that is free of asphaltenes and is typically passed to other conversion units such as a hydrocracking unit or a fluid catalytic cracking unit to produce lighter, more valuable fractions. 
     Deasphalted oil contains a high concentration of contaminants such as sulfur, nitrogen and carbon residue which is an indicator of the coke forming properties of heavy hydrocarbons and defined as micro-carbon residue (MCR), Conradson carbon residue (CCR) or Ramsbottom carbon residue (RCR). MCR, RCR, CCR are determined by ASTM Methods D-4530, D-524 and D-189, respectively. In these tests, the residue remaining after a specified period of evaporation and pyrolysis is expressed as a percentage of the original sample. For example, deasphalted oil obtained from vacuum residue of an Arabian crude oil contains 4.4 W % of sulfur, 2,700 ppmw of nitrogen, and 11 W % of MCR. In another example, a deasphalted oil of Far East origin contains 0.14 W % sulfur, 2,500 ppmw of nitrogen, and 5.5 W % of CCR. These high levels of contaminants, and particularly nitrogen, in the deasphalted oil limit conversion in hydrocracking or FCC units. The adverse effects of nitrogen and micro-carbon residue in FCC operations have been reported to be as follows: 0.4-0.6 W % higher coke yield, 4-6 V % less gasoline yield and 5-8 V % less conversion per 1000 ppmw of nitrogen. (See Sok Yui et al., Oil and Gas Journal, Jan. 19, 1998.) Similarly, coke yield is 0.33-0.6 W % more for each one W % of MCR in the feedstock. In hydrocracking operations, the catalyst deactivation is a function of the feedstock nitrogen and MCR content. The catalyst deactivation is about 3-5° C. per 1000 ppmw of nitrogen and 2-4° C. for each one W % of MCR. 
     It has been established that organic nitrogen is the most detrimental catalyst poison present in the hydrocarbon streams from the sources identified above. Organic nitrogen compounds poison the active catalytic sites resulting in catalyst deactivation, which in turn reduces catalyst cycle process length, catalyst lifetime, product yields, and product quality, and also increases the severity of operating conditions and the associated cost of plant construction and operations. Removing nitrogen, sulfur, metals and other contaminants that poison catalysts will improve refining operations and will have the advantage of permitting refiners to process more and/or heavier feedstocks. 
     In coking processes, heavy feeds are thermally decomposed to produce coke, gas and liquid product streams of varying boiling ranges. Coke is generally treated as a low value by-product. It is removed from the units and can be recovered for various uses depending on its quality. 
     The use of heavy crude oils having high metals and sulfur content as an initial feed is of interest due to its lower market value. Traditional coking processes using these feeds produce coke which has substantial sulfur and metal content. The goal of minimizing air pollution is a further incentive for treating residuum in a coking unit since the gases and liquids produced contain sulfur in a form that can be relatively easily removed. 
     While individual and discrete solvent deasphalting and coking operations are well developed and suitable for their intended purposes, there remains a need for improved processes using heavy feeds having asphaltenes, N, S and metal contaminants. 
     SUMMARY OF THE INVENTION 
     An integrated system and process is provided for producing liquid coker products, high quality petroleum green coke, and asphalt. An enhanced solvent deasphalting process 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 process is integrated so that the deasphalted oil with reduced contaminants is the coking unit feedstock, facilitating production coker liquid and gas fractions and recovery of petroleum green coke. 
     In certain embodiments of the integrated process, which can be carried out within refinery limits, use of the deasphalted oil intermediate stream as feed to the coking unit enables recovery of high quality petroleum coke 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). 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       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: 
         FIG. 1  is a process flow diagram of one embodiment of an integrated enhanced solvent deasphalting and coking process; and 
         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 
     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). 
     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. 
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                   
                   
                   
                 Calcined 
                 Calcined 
               
               
                   
                   
                 Fuel 
                 Sponge 
                 Needle 
               
               
                 Property 
                 Units 
                 Coke 
                 Coke 
                 Coke 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Bulk Density 
                 Kg/m 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 
               
               
                   
               
            
           
         
       
     
     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. 
     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. 
     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. 
     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. 
     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). 
     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. 
     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. 
     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. 
     Table 2 provides delayed coker operating conditions for production of certain grades of petroleum green coke in the process herein: 
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 2 
               
               
                   
               
               
                 Variable 
                 Unit 
                 Fuel Coke 
                 Sponge Coke 
                 Needle Coke 
               
               
                   
               
             
            
               
                 Temperature 
                 ° C. 
                 488-500 
                 496-510 
                 496-510 
               
               
                 Pressure 
                 Kg/cm 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 
               
               
                   
               
            
           
         
       
     
     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. 
     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. 
     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. 
     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. 
     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. 
     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. 
     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  70   a  and  70   b , and a coking product fractionator  80 . 
     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. 
     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. 
     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. 
     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 3  to C 7  paraffinic solvent. The following Table 3 provides critical temperature and pressure data for C 3  to C 7  paraffinic solvents: 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 3 
               
               
                   
                   
               
               
                   
                 Carbon Number 
                 Temperature, ° C 
                 Pressure, bar 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 C 3   
                 97 
                 42.5 
               
               
                   
                 C 4   
                 152 
                 38.0 
               
               
                   
                 C 5   
                 197 
                 34.0 
               
               
                   
                 C 6   
                 235 
                 30.0 
               
               
                   
                 C 7   
                 267 
                 27.5 
               
               
                   
                   
               
            
           
         
       
     
     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. &amp; 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&#39;s and dipole interactions measures the interaction energy of the liquid that is not impacted by changes in the orientation of the molecules. 
     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. 
     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 . 
     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&#39;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 . 
     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. 
     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  70   a  or  70   b . In certain embodiments, two or more parallel coking drums  70   a  and  70   b  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  70   a  or  70   b . Any hydrocarbon vapors remaining in the coke drum can be removed by steam injection. 
     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 . 
     The coke remaining in coker drum  70   a  or  70   b  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. 
     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. 
       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  170   a  and  170   b , and a coking product fractionator  180 . 
     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 3  to C 7  paraffinic solvent. 
     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 . 
     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&#39;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 . 
     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. 
     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 . 
     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  170   a  or  170   b . In certain embodiments, two or more parallel coking drums  170   a  and  170   b  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  170   a  or  170   b . Any hydrocarbon vapors remaining in the coke drum can be removed by steam injection. 
     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 . 
     The coke remaining in coker drum  170   a  or  170   b  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. 
     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. 
     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 &amp; 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. 
     
       
         
           
               
               
               
               
             
               
                 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 
               
               
                   
               
            
           
         
       
     
     DAO-SDA: Solvent deasphalted oil using conventional solvent deasphalting technology 
     DAO-ESDA: Solvent deasphalted oil using enhanced solvent deasphalting technology (with adsorbents) 
     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. 
     
       
         
           
               
               
               
               
             
               
                 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 
               
               
                   
               
            
           
         
       
     
     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 %. 
     The sulfur and metals levels are also calculated for the three feedstock and summarized in Table 6. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 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 
               
            
           
         
       
     
     As seen the deasphalted oil obtained from enhanced solvent deasphalting unit, which utilizes adsorbent, produces high coke meeting the anode grade coke specification. 
     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. 
     Table 7 shows the properties of the samples of petroleum green coke and Table 8 shows the properties of the calcium samples. 
     
       
         
           
               
               
               
               
               
               
             
               
                 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 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
             
               
                 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 
               
               
                   
               
            
           
         
       
     
     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.