PROCESS FOR UPGRADING RESIDUAL HYDROCARBON OILS

Abstract: Process for the electrophoretic removal of suspended inorganic solid particles from a residual hydrocarbon oil, said process comprising passing the residual hydrocarbon oil through one or more vessels, each comprising at least one electrode, in which vessel(s) the residual hydrocarbon oil is exposed to a DC electric field having an electric field strength of at least 0.4 kV/cm (1 kV/inch), whereby in total at least 10 % by weight of the initial amount of the selected inorganic solid particles, preferably iron species, are removed by attraction to an electrode. Suitably the treated residual oil is subsequently subjected to hydrodemetallization and hydrodesulphurization.

Description: PROCESS FOR UPGRADING RESIDUAL HYDROCARBON OILS The present invention relates to a process to upgrade crude oil residual by removal of suspended solids. Use of hydrocarbon fuels containing high levels of sulphur has become restricted in many parts of the world. For example, almost all residual fuels containing more than 1.6% by weight sulphur produced on the West Coast of the United States are exported from the United States due to the absence of a domestic market. High sulphur residual fuels have always commanded low prices, and the differential between prices of high sulphur and low sulphur products is expected to increase further in the future. Many processes are available to upgrade high sulphur residuals. But many refiners continue to sell low value residuals rather than to invest the capital required for these processes because of the shortcomings of these prior art processes. One of the most common residue upgrading processes is thermal cracking. Hereby lighter hydrocarbon products are produced, but also substantial amounts of coke, which is not a particularly high value product. Gasification type processes are known that convert the residual into gases. Sulphur can be easily removed from these gases, resulting in a clean fuel. But the major product of these gasification processes is a low BTU gas that generally does not have a high value due to availability of alternative fuels. Sulphur can be removed from residual oils by hydrodesulphuri- zation which usually involves contacting the residual oil with a hydrodesulphurization catalyst in the presence of hydrogen. Such processes are known in the art and can be operated in a fixed bed mode, an ebullating bed mode or in a moving bed or bunker flow mode. It is also known in the art that nickel and vanadium, commonly present in residual oils, cause deactivation of the hydrodesul- phurization catalyst. For this reason the residual oil is usually first subjected to a demetallization treatment in order to reduce its nickel and vanadium content prior to hydrodesulphurization. Demetallization catalysts become saturated with metals and must be eventually regenerated or replaced. Asphaltenes also tend to form coke on the catalyst and block pore openings and plug the 5 catalyst bed. Residual oil streams may contain solid, suspended iron species, such as iron sulphides and iron oxides in relatively small amounts, but these small amounts cause a significant problem when these streams are passed over demetallization catalysts. It has been 10 found that the iron compounds tend to deposit near pore openings in the demetallization catalysts, tending to rapidly block much of the catalyst's surface area. Once deposited, iron also promotes deposition of other inorganic solids, compounding the problem of pore blockage. 15 Other inorganic solids present in residual oils include metallic solids, such as sodium, magnesium, and calcium salts. For example, vacuum residuals from Chinese crude oils Chengbei, Shengli, and Yangsanmu were found to contain, respectively, 117, 39, and 25 ppm by weight calcium. These other metallic solids may also cause 20 pore plugging when such streams are passed over hydrotreating catalysts. Toluene insoluble organics (sludge) present in residual oils also plug catalyst pores. Catalysts and processes for hydrodemetallization and hydro¬ desulphurization of residual oils are disclosed in, for example, 2.5 U.S. Patent Nos. 4,908,344; 4,680,105; 4,534,852; 4,520,128; 4,451,354; 4,444,655; 4,166,026; and 3,766,058. The rate at which the demetallization catalyst in a fixed bed reactor loses activity is critical to the economics of each of these processes because of the costs involved in shutting down the process to replace the 30 catalyst. An improved commercial process for removal of metals from residual oils includes continuous addition and removal of demetallization catalyst from a reactor in order to achieve an acceptable time period between shutdowns and reasonably sized 35 reactor vessels. This is referred to as "bunkering" of catalyst. It will be evident that the presence in residual oils of solid iron species and other inorganic solids which cause deactivation of the demetallization catalyst can only be kept under control when applying a sufficiently high bunker rate, i.e. a sufficiently rapid continuous replacement of demetallization catalyst. It would therefore be advantageous to be able to apply a lower bunker rate by extending the catalyst life. Accordingly, there exists a considerable economic incentive to extend the life of the demetallization catalyst. Alternatively, it would also be very attractive to permit processing of residuals having higher initial levels of metals at the same bunker rate presently applied. Removal of solids from petroleum residual oil using a DC electric field having a field strength of at least 5 kiloVolts (kV) per inch, i.e. 2 kV/cm is disclosed in U.S. Patents 3,799,855 and 3,928,158. The petroleum residue is exposed to the electric field in a vessel containing a porous bed of non-conductive spheres, suitably glass beads, serving as an electrofilter. After solids have been deposited on the surface of the spheres due to the presence of the electrical field, the solids are removed from the spheres by removing the electrical field or reversing the electrical field polarity, and backflushing with a wash liquid. The liquid wash preferably includes a small amount of nitrogen gas to improve removal of solids from the spheres. This process becomes less suitable when large liquid throughput rates are required, as in residual oil conversion. In U.S. Patent 2,996,442 the removal of dissolved complex organo-metallic compounds from residual oils using DC electric fields is disclosed. The process described in this patent includes preheating the residue to a temperature from about 316 °C (600 °F) to about 482 °C (900 °F) for a time period of about 0.3 to about 10 hours subsequently diluting it with a solvent such as naphtha and then subjecting it to the DC electrical field. A precipitate is formed upon contact of the solvent with the preheated oil. The DC electrical field then removes the precipitate. Addition of the solvent requires a subsequent distillation step to recover the solvent. Such a distillation would be very expensive both in operating costs and capital costs. U.S. Patent 4,248,686 discloses a process to remove solids from a hydrocarbon stream using a filter over which a high voltage DC electrical field is applied. This patent discloses adding a surfactant such as a dioctyl sodium sulphosuccinate to the slurry to improve the electrophoretic mobility of solids in the slurry. Only surfactants in the sodium salt form are specifically mentioned, and use of such a surfactant in a process to remove metals from residual oil would undesirably increase the amount of sodium in the residual oil. Furthermore, no reference is made to treatment of residual oils. Accordingly, there is a need to provide a process wherein residual oils can be treated to effectively remove suspended metallic solids, particularly iron species, at economically viable throughput rates without the necessity of subsequent distillation steps to remove any diluents added. This need was also recognised in U S Patent No. 5,106,468. The aim underlying this patent specification was to provide a process wherein migration by electrophoresis of a dispersed phase in a continuous liquid phase, such as e.g. a residual oil, could be effected. No filterbed or diluent are necessary. A high conductivity, i.e. a conductivity above lO -0, (Ωm) ~ l, of the liquid to be treated was seen as a major difficulty for providing large scale electrophoretic separation processes. As is also evident from the afore-mentioned US Patent No. 3,928,158, residual oils have relatively high conductivities in the order of magnitude of 10"^ (Ωm) -1 . The solution offered in US Patent No. 5,106, 68 involves applying a specific asymmetric, time-dependent and periodic electric field across the liquid containing the dispersed solid contaminants, so that a net electrophoretic migration of the dispersed solid particles is accomplished causing these particles to accumulate in a collection region. However, the asymmetric periodic electric field to be applied puts stringent demands on equipment, particularly with respect to process control. It will be appreciated that such expensive equipment requires high capital investments and expenditure. Accordingly, there is a need to provide a process requiring less complex equipment, thus rendering the process less expensive, both in terms of initial investment and operating costs, whilst still effectively removing suspended inorganic solids from residual oils. It is therefore an object of the present invention to provide a process for effectively removing suspended solid inorganic particles, in particular iron species, from residual hydrocarbon oils by electrophoresis only, i.e. without needing to apply any non- conductive electrofilter material, in a commercially attractive manner, said process being very well controllable in a relatively simple way by using a DC electric field. It is a further object of the present invention to provide a method to remove metals in general from a residual oil utilizing a pretreatment of the residual oil with a DC electrical field. It is still a further object to provide such a method utilizing a demetallization catalyst wherein the demetallization catalyst is not consumed at a high rate. It is another object to provide such a method wherein the DC electrical field may be practically applied in a limited number of large scale vessels, allowing high oil throughput rates, and distillation of a solvent is not required. Accordingly, the present invention relates to a process for the electrophoretic removal of suspended inorganic solid particles from a residual hydrocarbon oil, said process comprising passing the residual hydrocarbon oil through one or more vessels, each comprising at least one electrode, in which vessel(s) the residual hydrocarbon oil is exposed to a DC electric field having an electric field strength of at least 0.4 kV/cm (1 kV/inch) , whereby in total at least 10% by weight of the initial amount of the selected inorganic solid particles, preferably iron species, are removed by attraction to an electrode. The expression "electrophoretic removal" as used in this connection implies that no non-conductive electrofilter material need to be applied for removing the suspended inorganic solids. Each vessel preferably provides a residence time of between 2 minutes and 6 hours, preferably between two minutes and two hours and one or more electrodes, the electrodes preferably having a total surface area of between 0.01 and 1.0 irr/ (ton/day) based on the total residual oil. The process of the present invention is suitably followed by a hydrodemetallization treatment of the electrophoretically treated oil, as the amount of inorganic solids which cause plugging of the pores of the hydrodemetallization catalyst has been significantly reduced. Hydrodemetallization catalysts often have shorter than desired lifes because catalyst pores become prematurely plugged with inorganic and organic solids. Organic solids include toluene insoluble material. Inorganic solids typically have a high iron content, and also contain significant amounts of inorganic salts such as sodium chloride, calcium salts and magnesium salts. Iron is typically present in the form of iron oxides and iron sulphides. These solids are effectively removed from residual oil streams by treatment with a DC electrical field according to the present invention prior to hydrodemetallization resulting in a significant increase in the useful life of the hydrodemetallization catalyst. The electrodes are preferably coated with a polymeric material to improve electrode cleaning rate. Preferred polymeric materials are siloxane polymers and tetrafluoroethylene polymers. Removal of solids from residual oil using the DC field of the present invention can be enhanced by addition of a surfactant to the residual oil. Fig. 1 is a plot of iron removal as a function of a severity factor for five residuals. Fig. 2 is a plot of iron removal as a function of the amount of residual treated. The residual oil that is treated in the method of the present invention is preferably an atmospheric residue (long residue) or a vacuum residue (short residue), but could be any stream that contains such products. For example, straight crude oil contains these bottoms products, as does thermally cracked or catalytically cracked heavy products. In any event, the residual oil has a relatively high content of asphaltenes. Preferably, the residual oil is a heavy asphaltenes-containing hydrocarbonaceous feed comprising at least 35% by weight, preferably at least 75% by weight and more preferably at least 90% by weight, of hydrocarbons having a boiling point of 520 °C or higher. Accordingly, the residual oil is preferably an atmospheric residue or a vacuum residue, also because these streams are essentially free of water as a result of the prior distillation and contain relatively high concentrations of solids because the prior distillation has reduced the total volume of the streams but has not removed solids. The present invention removes more than ten percent by weight of a selected inorganic solid. Preferably, greater than 50% of the original amount of selected inorganic solid is removed from the oil. The selected inorganic solid is a component such as, for example, iron, calcium, sodium, or magnesium. A significant portion of toluene insoluble organic solids, other inorganic solids and some asphaltenes are also removed by exposing the residual oil to a DC electrical field. Removal of iron can be used as an indicator of the removal of inorganic solids and toluene insoluble solids. Because iron removal can be determined with better accuracy, selection of iron as the selected inorganic solid of the present invention is preferred. When iron removal is measured, it will be understood that inorganic solids and toluene insoluble organic solids in general are removed to at least some extent and preferably to a significant extent. The initial amount of iron in the residual oil may be, for example, between about 5 and about 150 parts per million (ppm) by weight. Lesser amounts of the selected inorganic solid may be tolerated by fixed or bunkered beds of hydrodemetallization catalysts, and greater amounts of the selected inorganic solid may be more economically removed using other methods. Considerable improvements to hydrodemetallization catalyst lifes can be realized when more than ten percent by weight of the selected inorganic solid is removed from the residual oil prior to passing the residual oil over the hydrodemetallization catalyst. Preferably 50% or more of the selected inorganic solid initially present is removed from the residual oil by exposing the residual oil to the DC electrical field in accordance with the present invention. Accumulation of solids on the electrode(s) will eventually reduce the effectiveness of the electrical field for such removal. Preferably before a significant part of the electrode's effectiveness is lost, solids may be removed from the electrodes by discontinuing or reversing the electrical field and flushing with a fluid such as a gas oil or slurry oil. Reversal of the electrical field enhances solids removal. A plurality of vessels containing electrodes for application of the DC field are preferably provided so that the vessels may be removed from residual oil treating service for the solids removal operation without interruption of residual oil treating process. This can for instance be achieved by placing the vessels in series whereby each vessel can be bypassed independently. Accordingly, a vessel can then be bypassed when its electrodes are being cleaned, whilst at the same time maintaining the flow of residual oil through the other vessel(s). Alternatively, the vessels can be arranged in a parallel mode, whereby the flow of residual oil to each vessel can be interrupted when cleaning of the electrodes in a vessel is necessary. At the same time the flow of residual oil to the other vessels can then be maintained. An alternative electrode cleaning method is to discontinue or reverse the electrical field, and use residual oil feed as the flushing fluid. The solids laden residual oil exiting the vessel can be routed to an alternate disposition during the cleaning cycle without otherwise interrupting the operation of the vessel. The electrodes are preferably coated with a polymer to enhance electrode cleaning rates. The polymer is preferably one that can be applied in a thin coating, so that the electrical field strength is minimally impaired. The polymer is also preferably capable of withstanding desired electrode operating temperatures. Particularly preferred polymers include tetrafluoroethylene polymers, siloxane polymers, and epoxy resins. Coatings of these polymers are readily available in forms that can be applied to electrodes such as stainless steel electrodes by brushing, dipping the electrode in a solvent containing the polymers, or by spraying the coating onto the electrode. A suitable tetrafluoroethylene polymer is "CAMIE 2000TFA COAT" (trademark) sold by DuPont, and a suitable siloxane polymer is "AMERCOAT 738" (trademark) sold by Amron Co. The electrodes are preferably parallel plates stacked in a vertical vessel with the plates parallel to the residual oil flow, with between 2.5 and 10 cm (1 and 4 inch) spacing between the plates. About 5 cm (2 inch) spacing between plates is preferred. About 5 cm (2 inch) spacing is sufficient to prevent shorting of the plates due to sloughing of small amounts of solids, and still results in a sufficient amount of electrode surface area within a volume that results in a preferred residence time. The time period before loaded electrodes must be cleaned will be about proportional to the surface area of electrodes upon which the solids may accumulate. Having sufficient electrode surface area allows one to five days of continuous operation between times when solids must be removed from the electrodes. The surface area of the electrodes, including both the positive and the negative electrodes, is preferably between 0.01 and 1.0 m^/ (ton/day) and more preferably between 0.05 and 0.4 m.2/ (ton/day) based on total amount of residual oil in order to provide a reasonable time period between electrode cleaning operations. The parallel plate electrode configuration is simple and readily scaled up to a capacity that could be of commercial applicability. The parallel plate electrodes may be corrugated or flat plates. Plates having vertical corrugations are preferred because the flow of residual oil will be more uniform through the plates if they are corrugated. Corrugated plates also provide more strength for the weight of the plate, and therefore plates of similar thickness would have less tendency to buckle. The charge on the plates are alternated so that each side of the plates functions as an electrode and provides surface area upon which solids can accumulate. The electrodes could be of other shapes, such as rods or cylinders. A very suitable configuration, for instance, is a cylindrical anode with a cathode rod centered along the longitudinal axis of the anode. The cylindrical anode may at the same form the vessel in which the DC treatment takes place, so that only one electrode (the rod) needs to be placed inside the vessel. Alternatively, the cylindrical anode and cathode rod are located inside a separate vessel. Of course, it is also possible to use a cylindrical cathode with an anode rod centered along the longitudinal axis of the cylinder. Other configurations may be applied as well, as long as they allow a DC field to be adequately applied. The vessel is preferably vertical and has a residence time of between 2 minutes and 6 hours, preferably between 2 minutes and 2 hours, and more preferably between 5 minutes and 30 minutes. As already explained above, multiple vessels are preferred, the vessels providing sufficient volume so that one of the vessels may be taken off-line individually for removal of accumulated solids from the electrodes without impairing residual oil throughput at preferred residence times. The residual oil is preferably treated by the DC field when the residual oil is at a temperature that permits acceptable mobility of solids within the residual oil. Typically, this will require a temperature of between 93 β C (200 °F) and 371 β C (700 °F) for atmospheric column bottoms or vacuum flasher bottoms. A temperature of between 149 °C (300 °F) and 316 β C (600 °F) is preferred. Removal of solids generally increases with increasing DC electric field strength. The maximum field strength is limited by the conductivity of the residual oil. It has been surprisingly found that solids can be separated from residual oils at considerably higher conductivities than from other hydrocarbons using a DC electric field. A possible explanation for this observation is that the conductivity of residual oils is to a significant extent caused by the relatively high amount of asphaltenes present. In practice, this means that the DC electric field has a field strength of at least 0.4 kV/cm (1 kV/inch) , preferably between 0.8 and 8 kV/cm (2 and 20 kV/inch) and more preferably between 2 and 6 kV/cm (5 and 15 kV/inch) . Surfactants may be added to the residual oils to enhance removal of organic or inorganic solids by the DC electrical field of the present invention. The surfactant is preferably an oil soluble anionic surfactant such as an diammonium laurylsulphate or an ammonium alkylsulphosuccinate. Anionic surfactants in the form of ammonium salts are most preferred because the ammonium salts do not add additional metal ions to the residual oils that could be detrimental to downstream catalysts. Concentrations of between about 5 and about 100 ppm by weight of surfactant, based on the total residual oil, is preferred when surfactants are used. The DC electrical field of the present invention also removes some asphaltenes from the residual oil. This can be an advantage because asphaltenes tend to form coke on fixed bed catalysts. The residence time of the residual oil in the present invention may be sufficient to result in removal of at least about one third of the asphaltenes present in the initial residual oil. If it is desired to remove asphaltenes, it has been found that addition of surfactants to the residual oil is particularly effective to improve removal of asphaltenes. Because hydrodemetallization catalysts can be economical and effective for removal of asphaltenes, it may be preferable to adjust the residence time, temperature, the concentration of a surfactant, or the strength of the DC field to effectively remove inorganic solids, but not asphaltenes. This would significantly decrease electrode fouling while not significantly decreasing downstream catalyst activities. The hydrodemetallization catalyst through which the residual oil may be passed after at least ten percent of the selected inorganic solid has been removed by the DC electrical field in accordance with the present invention, may be any of those known to be useful for hydrodemetallization of residual oils by those of ordinary skill in the art. Each of these known catalysts benefits from removal of solids prior to passing the residual oils over the catalyst. After the residual oil is subjected to hydrodemetallization, the residual oil is then preferably further processed to increase the value of the products. Desulphurization and denitrification by known processes can improve the residual oil's properties as either a fuel or as a feed for a further conversion process. Further conversion processes will generally be either a fluidized bed catalytic cracking process or a hydrocracking process using a catalyst in a fixed bed reactor. The invention is further illustrated by the following examples. Example 1 The effectiveness of a DC electrical field in removal of iron components from residual oils was demonstrated by passing different residual oils through a cylindrical vessel having a cylindrical anode having an inside diameter of 4.6 cm (1.8 inches) and a length of 6.6 cm (2.6 inches) and a 0.3 cm (1/8-inch) diameter cathode rod centered in the longitudinal axis of the anode. An Arabian Heavy long residue having an initial iron content of about 18 ppm by weight was passed through the DC field at a flowrate that resulted in a residence time of 0.9 hours. The residue was preheated to a temperature of 177 °C (350 °F) . The iron content of the residue was reduced to about 2.5 ppm with a 10 kV difference between the electrodes (i.e. an electric field strength of 4.7 kV/cm) and about 7.5 ppm with 5 kV difference between the electrodes (i.e. an electric field strength of 2.4 kV/cm) . The solids accumulated on the electrodes included iron, present as iron oxide and iron sulphide, and sodium, present mostly as sodium chloride, and toluene insoluble organic material. Example 2 Static experiments were carried out in cylindrical cells equipped with two flat plate electrodes. The flat plates were 1.7 cm (11/16 inches) apart. Each plate had a length of 6.88 cm (2.71 inches) and a width of 2.8 cm (1.1 inches). The cell was filled with oil and DC potential was then placed across the electrodes for the test residence time. Tests were performed under the following conditions: temperatures ranging from 93 "C-371 °C (200 °F-700 °F) ; DC potentials or voltages of from 2-7 kV; and residence times ranging from 5 minutes to 5 hours. Upon completion of each test the electrodes were removed and the oil was analyzed with respect to the concentration of inorganic and organic particles. Five different residual oils were exposed to the DC electric fields in this series of experiments. Fig. 1 is a plot of the fraction of iron removed versus a severity factor where the severity factor is residence time in hours times the applied voltage in kV divided by the residue viscosity in centistokes. Because the electrode spacing was identical for each of these tests, the electrical field strength is proportional to the voltage applied between the electrodes. The five residues and the lines on Fig.l that correspond to the residues were: Arabian Heavy Long Residue ("AHL")(1), Arabian Heavy Short Residue ("AHS")(1), Oman Long Residue ("OL") (2), Kirkuk/Kuwait Short Residue ("KKS") (3) , and Kuwait Long Residue ("KL") (4) . The Arabian Heavy Long and the Arabian Heavy Short are represented by the same line. TABLE 1 below lists metal contents, C5 asphaltenes and viscosities of these residues (kinematic viscosity in Centistokes, Cst) at certain temperatures @ in "C. TABLE 1 Composition KKS AHS AHL ____ OL (ppmw) Al 3 4 <2 <1 3 Ca <1 6 <1 2 3 Co <1 <1 <1 <1 <1 Cr 2 2 <1 <1 <1 Fe 19 38 18 19 16 K <1 <1 <1 <1 <1 Mg <1 6 <1 <1 <1 Mo 2 2 <1 <1 <1 Na 11 39 24 2 1 Ni 56 52 27 13 9 Si <1 <1 <1 <1 <1 V 164 164 83 42 11 Zn 2 3 2 2 1 C 5 Asphalte¬ 25.9 20.4 11.6 5.5 2.72 nes, %w Viscosities, Cst @ "C 1407 @125 1407 @125 166 eioo 7189 023 2248 @27 378 6150 444 @150 28 @150 452 @52 794 @38 141 @175 160 8175 16 S175 239 @61 345 @49 From Fig. 1 it can be seen that about 80% of the iron in each residue can be removed at a sufficient severity for each of the five residues although the severity required to obtain a target level of iron removal differs between residues. Example 3 The rate at which electrodes will foul and cause a decrease in the performance of the apparatus of Example 1 was determined by operating the apparatus at a residue feed rate that resulted in about a ten minute residence time at a temperature of about 199 °C (390 °F) . Fig. 2 is a plot of the iron content of the treated residue as a function of the amount of residue treated per unit of electrode surface area. From Fig. 2 it can be seen that the iron in the treated residue gradually increased as more residue was processed. It was further found that after the electrodes were rinsed with gas oil with the electrical field removed, performance of the electrodes consistently returned to a start-of-run effectiveness. Example 4 Removal of iron and other metals was demonstrated using the apparatus of Example 2. AHS residue was treated with a severity of 12.5 kV-min/Cst and at 316 °C (600 °F) . The applied voltage was 5 kV and the residence time was 30 minutes. Initial and treated oil metals content in parts per million by weight (ppmw) are listed in Table 2 below. TABLE 2 ppmw Initial Treated Al 4 <3 Ca 6 2 Fe 39 5 Mg 6 3 Mo 2 2 Ni 52 52 Na 39 16 V 164 163 Zn 3 <1 Ash (%wt) 0.057 0.046 From Table 2 it can be seen that concentrations of metals other than nickel, vanadium and molybdenum are significantly reduced. Nickel and vanadium are present mostly associated with asphaltenes, and are not significantly removed. These metals are conveniently removed by hydrodemetallization. Example 5 Tests were run as described above in Example 2 with three different anionic surfactants added to KKS residual oil. The tests were run at a temperature of 260 °C (500 °F) with five hours residence time and a five kV differential potential, resulting in a severity of about 62.5 kV-min/Cst at this example's electrode geometry. The surfactants and the results are listed in Table 3 below. TABLE 3 Surfactant Type Surf. Iron in (ppm) Residue (ppm) None N/A N/A 17 Mackanate LA diammonium laurylsul- phosuccinate 2000 9 Rhodapon L-22 ammonium lauryl- sulphate 2000 10 Stepanol AM ammonium lauryl- sulphate 2000 2 Mackanate LA diammonium lauryl- sulphosuccinate 100 9 From Table 3 it can be seen that each of the three surfactants were effective in improving the removal of iron by the DC field, and that the concentration of effective surfactant needed may be below 100 ppm. It can also be seen from the results in Table 3, and the results of Examples 2 and 3, that a severity of about ten to about fifty kV-min/Cst would be sufficient to achieve maximum solids removal from many common residues. Although some residues may require greater severity, these residues may be treated by addition of a surfactant to result in a residue from which about ten percent or more of the iron could be removed using a severity of between 2 and 50 kV-min/Cst. Example 6 Tests were performed to determine the effect of high levels of surfactant using the apparatus of Example 2. The surfactant used was ASA-3, available from Royal Lubricants Company, Inc. of East Hanover, N.J. This surfactant is marketed as an antistatic jet fuel additive and is a solution in xylene of chromium and calcium organic salts stabilized with a polymer. A residence time of two hours was used, a temperature of 316 C C (600 °F) , a five kV power differential, and KKS residual oil. The metals content of the treated KKS residual is listed below in Table 4. TABLE 4 TEST ] No. 1 2 3 ASA-3 %wt 0.2 0.5 1.0 ppmw Ca 5 14 24 Cr 6 6 7 Fe 15 8 6 Ni 54 48 40 Na 13 13 14 V 162 129 130 Zn 1 1 1 From Table 4 it can be seen that ASA-3, at increasing concentrations, increases removal of the vanadium and nickel, which are normally associated with asphaltenes. Calcium, in particular, appears to be added to the residual oil with the ASA-3 because the level of calcium in the treated oil increases with the addition of ASA-3. Example 7 The effectiveness of a polymeric coating to improve the cleaning of the electrode was demonstrated by conducting static experiments in the cell described in Example 2 with the electrodes coated with "CAMIE 2000 TFA COAT" sold by DuPont. This is a tetrafluoroethylene polymer coating. Arabian Heavy Long Residue was placed in the cell for two hour cycles at 149 °C (300 °F) , with fresh residue for each cycle. After three cycles, the electrodes were covered with a layer of solids. The electrodes were then placed in a 177 C C (350 °F) gas oil bath without electrical power applied. After five minutes, the electrodes were free of solids. A comparative experiment was performed with the same procedure except uncoated stainless steel electrodes were used. The uncoated stainless steel electrodes collected a similar amount of solids after three cycles, but after being in the gas oil bath for an hour, still were coated with some solids. This experiment demonstrated the effectiveness of a polymeric coating in improving the cleaning of the electrode.

Claims: C L A I M S 1. Process for the electrophoretic removal of suspended inorganic solid particles from a residual hydrocarbon oil, said process comprising passing the residual hydrocarbon oil through one or more vessels, each comprising at least one electrode, in which vessel(s) the residual hydrocarbon oil is exposed to a DC electric field having an electric field strength of at least 0.4 kV/cm (1 kV/inch) , whereby in total at least 10% by weight of the initial amount of the selected inorganic solid particles, preferably iron species, are removed by attraction to an electrode. 2. Process according to claim 1, wherein the residence time of the residual hydrocarbon oil in the vessel is in the range of from 2 minutes to 6 hours, preferably from 2 minutes to 2 hours. 3. Process according to claim 1 or 2, wherein the electrode(s) have a total surface area in the range of from 0.01 to 1 m^/ (ton/day) based on the total amount of residual hydrocarbon oil. 4. Process according to any one of the preceding claims, wherein a plurality of vessels are provided and metals attracted to the electrode are removed by discontinuing or reversing the electrical field and flushing the metals from the vessel using a flushing fluid. 5. Process according to claim 4 wherein the flushing fluid is selected from the group consisting of gas oil, residual oil and slurry oil. 6. Process according to any one of the preceding claims, wherein the vessel comprises a plurality of parallel electrode plates spaced between about one and about four inches apart. 7. The process of claim 6 wherein the electrode plates are corrugated plates. 8. Process according to any one of the preceding claims further comprising the step of adding to the residual oil, prior to passing the residual oil through the vessel, an amount of surfactant effective to improve removal of the suspended inorganic solid particles, in particular of suspended iron species. 9. The process of claim 8 wherein the effective amount of surfactant is about 5 to about 100 ppm by weight of residual oil. 10. The process of claim 8 or 9 wherein the surfactant is selected from the group consisting of ammonium laurylsulphate and ammonium alkylsulphosuccinate. 11. Process according to any one of the preceding claims, wherein the residence time of the residual oil in the vessel in minutes times the applied electric field strength in kVolts per cm divided by the viscosity of the residue stream at the temperature at which the residue when it is passed through the vessel in centistokes is between 5 and 125. 12. Process according to any one of the preceding claims, wherein passing the residual oil through the vessel results in at least half of the suspended inorganic solid particles being removed by passing the residual oil stream through the vessel. 13. Process according to any one of the preceding claims wherein the residual oil is passed through the vessel at a temperature of between 93 °C and 371 °C. 14. Process according to any one of the preceding claims wherein the residence time of the residual oil in the vessel is between five minutes and thirty minutes. 15. Process according to any one of the preceding claims, wherein each electrode has a polymer coated surface. 16. The process of claim 15 wherein the polymer is selected from the group consisting of a tetrafluoroethylene polymer, a siloxane polymer and an epoxy resin. 17. Process according to any one of the preceding claims further comprising the step of passing the treated residual oil over a hydrodemetallization catalyst under hydrodemetallization conditions. 18. The process of claim 17 further comprising the step of passing the residual oil over a hydrodesulphurization catalyst under hydrodesulphurization conditions.

Inventors: KRUKA VITOLD RAYMOND, WIELERS ANTONIUS FRANZISKUS HE, KRUKA, VITOLD, RAYMOND, WIELERS, ANTONIUS, FRANZISKUS, HEINRICH
Applicants: SHELL CANADA LTD, SHELL INT RESEARCH, SHELL CANADA LIMITED, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1995
Main classification: C10G32
IPC codes: C10G32, C10G45, C10G67