US3716479A - Demetalation of hydrocarbon charge stocks - Google Patents

Demetalation of hydrocarbon charge stocks Download PDF

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US3716479A
US3716479A US00100931A US3716479DA US3716479A US 3716479 A US3716479 A US 3716479A US 00100931 A US00100931 A US 00100931A US 3716479D A US3716479D A US 3716479DA US 3716479 A US3716479 A US 3716479A
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hydrogen
catalyst
charge stock
demetalation
nodules
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P Weisz
A Silvestri
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Mobil Oil AS
ExxonMobil Oil Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00—Chemistry of inorganic compounds
    • Y10S423/04—Manganese marine modules

Definitions

  • ABSTRACT This specification discloses the clemetalation of a hydrocarbon charge stock.
  • the demetalation procedure involves contacting the hydrocarbon charge stock with hydrogen in the presence of, as a catalyst, a material derived from the naturally-occurring underwater deposit known as a manganese nodule.
  • the manganese nodule may be employed without pretreatment or may be pretreated by sulfiding or by leaching to remove and recover one or more valuable metallic constituents.
  • the manganese nodule catalyst after it has become deactivated by use, may be processed to remove and recover one or more valuable metallic constituents.
  • U.S. Pat. No. 3,509,041 discloses the use of manganese nodules, after pretreatment by base exchange to bond hydrogen ions thereto, in hydrocarbon conversion reactions, specifically cracking, hydrocracking, oxidation, olefin hydrogenation, and olefin isomerization.
  • U.S. Pat. No. 3,471,285 discloses the selective separation of manganese and iron from manganese nodules which also contain cobalt and nickel by reducing the nodules at elevated temperatures and then leaching with an aqueous solution of ammonium sulfate.
  • a hydrocarbon charge stock is demetalized by contacting the charge stock with hydrogen, in the presence of, as a catalyst, a material derived from the naturally-occurring underwater deposit known as a manganese nodule.
  • the manganese nodule is employed without pretreatment.
  • the manganese nodule may be pretreated by sulfiding, or by leaching to remove one or more metallic constituents, or by any combination of the pretreating procedures.
  • the catalyst after becoming deactivated by use, is treated to remove and recover therefrom one or more metallic constituents.
  • FIGS. 1 and 2 of the accompanying drawings are photomicrographs of the surfaces of the manganese nodules.
  • FIG. 3 is a flow diagram illustrating a procedure wherein demetalation of a hydrocarbon charge stock is carried out and the charge stock is then processed for sulfur and/or nitrogen removal.
  • FIG. 4 is a flow diagram illustrating a procedure wherein demetalation of a hydrocarbon charge stock is carried out and the charge stock is then subjected to catalytic cracking.
  • Various hydrocarbon charge stocks such as crude petroleum oils, topped crudes, heavy vacuum gas oils, shale oils, oils from tar sands, and other heavy hydrocarbon fractions such as residual fractions and distillates contain varying amounts of non-metallic and metallic impurities.
  • the non-metallic impurities include nitrogen, sulfur, and oxygen and these exist in the form of various compounds and are often in relatively large quantities.
  • the most common metallic impurities include iron, nickel, and vanadium.
  • other metallic impurities including copper, zinc, and sodium are often found in various hydrocarbon charge stocks and in widely varying amounts.
  • the metallic impurities may occur in several different forms as metal oxides or sulfides which are easily removed by single processing techniques such as by filtration or by water washing.
  • the metal contaminants also occur in the form of relatively thermally stable organo-metallic complexes such as metal porphyrins and derivatives thereof along with complexes which are not completely identifiable and which are not so readily removed.
  • the presence of the metallic impurities in the hydrocarbon charge stocks is a source of difficulty in the processing of the charge stocks.
  • the processing of the charge stock whether the process is desulfurizing, cracking, reforming, isomerizing, or otherwise, is usually carried out in the presence of a catalyst and the metallic impurities tend to foul and inactivate the catalyst to an extent that may not be reversible. Fouling and inactivation of the catalyst are particularly undesirable where the catalyst is relatively expensive, as, for example, where the active component of the catalyst is platinum. Regardless of the cost of the catalyst, fouling and inactivation add to the cost of the processing of the charge stock and therefore are desirably minimized.
  • Demetalation of the hydrocarbon charge stock can be effected by thermal processing of the charge stock.
  • thermal processing results in conversion of an appreciable portion of the charge stock to coke and the portion of the charge stock converted to coke represents a loss of charge stock that desirably should be converted to a more economically valuable product or products.
  • the metallic impurities tend to deposit in the coke with the result that the coke is less economically desirable than it would be in the absence of the metals.
  • Demetalation can also be effected by catalytic hydroprocessing of the charge stock.
  • catalytic hydroprocessing results in the catalyst becoming fouled and inactivated by deposition of the metals on the catalyst. There is no convenient way of regenerating the catalyst and it ultimately must be discarded. Since these catalysts are relatively expensive, catalytic hydroprocessing to demetalize hydrocarbon charge stocks has suffered from adverse economics.
  • Manganese nodules are naturally occurring deposits of manganese, along with other metals, including iron, cobalt, nickel, and copper, found on the floor of bodies of water. They are found in abundance on the floors of oceans and lakes. For example, they are found in abundance on the floor of the Atlantic and Pacific Oceans and on the floor of Lake Michigan.
  • the nodules are characterized by a large surface area, i.e., in excess of 150 square meters per gram.
  • the nodules have a wide variety of shapes but most often those from the oceans look like potatoes. Those from the floor of bodies of fresh water, such as the floor of Lake Michigan, tend to be smaller in size. Their color varies from earthy black to brown depending upon their relative manganese and iron content.
  • the nodules are porous and light, having an average specific gravity of about 2.4. Generally, they range from one-eighth inch to 9 inches in diameter but may extend up to considerably larger sizes approximating 4 feet in length and 3 feet in diameter and weighing as much as 1,700 pounds.
  • the modules contain silicon, aluminum, calcium and magnesium, and small amounts of molybdenum, zinc, lead, vanadium, and rare earth metals.
  • the chemical and physical properties of manganese nodules are, as compared with conventional catalytic agents for this purpose, considered to be somewhat unusual.
  • the nodules have a high surface area, about l-250 square meters per gram. They will, however, lose surface area by metal deposition during the demetalation reaction. Further, as shown by Roger G. Burns and D. W. Fuerstenau in American Mineralogist, Vol.
  • FIGS. 1 and 2 are photomicrograph of a surface of the nodules, FIG. 1 showing more of the pore system than FIG. 2.
  • Magnifications in each figure are l5OX.ln each of the figures, the large dark areas are large pores. The lightand dark-banded regions are solid material.
  • the nodules are formed by slow deposition of colloidal materials. The composition of the particles of the colloidal materials varies with time resulting in the microscopic stratification and inhomogeneity shown in the figures.
  • the manganese nodules can be employed as the catalyst for the demetalation of the hydrocarbon charge stock substantially as mined, or recovered, from the floor of the'body of water in which they occurred.
  • the nodules, as mined, possibly after washing to remove sea water or lake water therefrom and mud or other loose material from the surface of the nodules, may be employed for demetalation.
  • the demetalation reaction may also be carried out employing, as the catalyst, manganese nodules which have been subjected to a pretreatment.
  • Pretreatments to which the manganese nodules may be subjected include sulfiding or leaching to remove therefrom one or more components of the nodules.
  • Sulfiding of the manganese nodules increases the extent of demetalizing of the charge stock. It also can increase the extent of desulfurization and Conradson Carbon Residue (CCR) reduction, each of which is desirable.
  • This treatment is carriedout by contacting the nodules with hydrogen sulfide.
  • the hydrogen sulfide may be pure or may be mixed with other gases. However, the hydrogen sulfide should be substantially free of hydrogen.
  • the temperature of sulfiding may be from about 300 F. to about 450 F. and the time of sulfiding may be from about 4 to about 8 hours.
  • the sulfiding may be effected, for example, by passing the hydrogen sulfide over the manganese nodules continuously during the sulfiding reaction.
  • the space velocity of the hydrogen sulfide is not critical and any space velocity compatible with the equipment and such that some hydrogen sulfide is continuously detected in the exit stream is suitable.
  • the manganese nodules may also be pretreated by being subjected to leaching to remove therefrom one or more components.
  • the manganese nodules contain, in addition to manganese, copper, nickel, and molybdenum. They may be pretreated to leach therefrom the copper, nickel, or molybdenum,or any two, or all three, of these metals.
  • the manganese nodules contain the copper, nickel, and molybdenum in sufficient quantities to provide a commercial source of these metals. Further, the removal, at least partially, of these metals and other of the metallic constituents of the nodules has apparently no effect on the catalytic activity of the nodules for demetalation of hydrocarbon charge stocks.
  • copper, nickel, and molybdenum, and other metals may be recovered from the nodules for the economic advantage to be gained by such recovery and the remainder of the manganese nodules can then be employed as a catalyst for demetalation of hydrocarbon charge stocks.
  • Removal of the copper and the nickel may be effected by leaching the manganese nodules with an aqueous solution of a strong acid.
  • strong acid is meant such acids as hydrochloric, sulfuric, and nitric acids.
  • the molybdenum may be removed from the manganese nodules by leaching them with aqueous base solutions such as aqueous solutions of sodium hydroxide or sodium carbonate. These solutions should have a pH of at least 8 and preferably should have a pH of at least 10.
  • the leaching with the aqueous base solutions can be carried out at ambient temperatures or at the boiling point of the solution.
  • the nodules may be crushed and sized to obtain a desired particle size depending upon the type of demetalation operation employed, for example, a fixed bed operation, an ebullition operation or otherwise.
  • the demetalation reaction is carried out by contacting the hydrocarbon charge stock simultaneously with the catalyst and with hydrogen.
  • the temperatures at which the reaction is carried out can be from about 650 F. to about 850 F. At the higher temperatures, a greater degree of demetalation occurs. However, the temperatures employed should not be so high as to effect an undesirable degree of alteration of the charge stock. Preferably, the temperatures employed are in the range of 750-850 F.
  • the pressures at which the reaction is carried out can be from about 100 to about 3,000 pounds per square inch gage (psig). Preferably, the pressures employed are in the range of 500-2,000 psig.
  • the liquid hourly space velocity (LHSV) of the charge stock can be from about 0.2 to 4, preferably 0.5 to 2, volumes of charge stock per volume of catalyst per hour.
  • Hydrogen circulation is at rates of 2,000-1S,000, preferably 5,000l0,000, standard cubic feet of hydrogen per barrel of hydrocarbon charge stock.
  • the hydrocarbon charge stock along with the hydrogen may be passed upwardly through a fixed bed of the catalyst in an upflow reactor or may be passed downwardly through a fixed bed of the catalyst in a downflow trickle-bed reactor.
  • the reaction may also be carried out by passing the charge stock and the hydrogen through an ebullient bed of the catalyst.
  • the reaction may also be carried out by contacting the charge stock, the hydrogen, and the catalyst in a batch reactor.
  • the catalyst after being employed in the demetalation reaction and having become catalytically deactivated, or spent, can be treated for the recovery therefrom of valuable metals.
  • the catalyst after becoming spent, may be treated to recover copper, nickel, molybdenum, or any two, or all three, of these metals. It may also be treated to recover therefrom any other component.
  • An advantage of the process of the invention resides in its economy with respect to hydrogen consumption.
  • hydrogen is consumed and the consumption of the hydrogen adds to the cost of demetalation.
  • reduction in the consumption of the hydrogen is economically desirable.
  • Prior processes directed to demetalation have often required consumption of hydrogen in amounts between about 450 and 1,000 cubic feet per barrel of hydrocarbon charge stock.
  • effective demetalation can be effected in many instances with consumption of 50 to 300 cubic feet of hydrogen per barrel of hydrocarbon charge stock.
  • the manganese nodules in the presence of sulfur, have essentially no activity for hydrogenating benzene and other aromatic molecules. They will, however, hydrogenate olefins. Hydrocarbon charge stocks contain sulfur to a greater or lesser extent, and, regardless of whether the catalyst is subjected to a sulfiding pretreatment, the sulfur in the hydrocarbon charge stocks will effect a rapid sulfiding of the nodules. As a result, hydrogenation of the aromatic constituents of the charge stock is reduced with resulting reduction in the consumption of the hydrogen.
  • sulfiding pretreatment of the nodules is of value. It is believed that, under reducing conditions, a reduction of the metal oxides in the nodules can occur with consequent loss in surface area and diminished activity. The sulfides on the other hand are more stable to reduction. Thus, when the nodules are exposed to a reducing environment either before or during sulfiding as occurs when the sulfiding results from the sulfur in the charge stock, a prereduction or competitive reduction of the oxides can take place.
  • the process of the invention may be employed for the demetalation of any hydrocarbon charge stock containing organo-metallic compounds.
  • these will be hydrocarbon charge stocks containing sufficient metal to cause difficulty in the processing, or other subsequent use, of the charge stocks.
  • Other subsequent use of the charge stocks can include burning of the charge stock as fuel wherein the metals cause corrosion problems.
  • These charge stocks include whole crude petroleum oils, topped crude oils, residual oils, distillate fractions, heavy vacuum gas oils, shale oils, oils from tar sands, and other heavy hydrocarbon oils.
  • Charge stocks derived from Mid-Continent and East Texas crudes contain small amounts of metals. For example, some East Texas crudes contain about 0.1 part per million of vanadium and 2-4 ,parts per million of nickel.
  • the process of the invention can be carried out in conjunction with subsequent steps of processing of the hydrocarbon charge stock.
  • the hydrocarbon charge stock can be subsequently processed for removal of sulfur and/or nitrogen.
  • the hydrocarbon charge stock can be subsequently processed by catalytic cracking.
  • the desulfurization catalyst suitable for use in such a combination process is broadly characterised as any hydrogenation catalyst which is tolerant of sulfur and nitrogen and which can be employed in an operating cycle or onstream life that is economically attractive.
  • the desulfurization and/or denitrogenation catalyst may be any one of those known and used for such purposes in the prior art.
  • Prominent catalysts used for this purpose include cobalt molybdate on alumina with or without small amounts of silica, nickel sulfide, tungsten sulfide, and nickel-tungsten sulfide alone or on a support material such as alumina which may or may not contain small amounts of combined silica.
  • Other suitable and known desulfurization catalysts may also be employed.
  • a relatively heavy hydrocarbon feed such as a residual oil containing sulfur and metal contaminants is introduced to the process through line 10 to furnace 11 wherein the hydrocarbon feed is heated to an elevated temperature in the range of from about 650 F. to about 850 F.
  • the hydrocarbon feed may be heated either alone or in combination with hydrogen rich gas supplied through line 12, it being preferred to mix the hydrogen rich gas with the feed prior to being heated in the furnace.
  • the heated mixture is introduced through line 13 'to demetalation reactor 14.
  • Make-up fresh catalyst may be added with the hydrocarbon feed through line 15 or directly to the demetalation reactor.
  • the demetalation reactor can be operated under liquid phase conditions wherein finely divided manganese nodules are added to and maintained in suspended motion by the liquid hydrocarbon flowing upwardly through the demetalation reactor.
  • the rate of flow of the liquid feed upwardly through the demetalation reactor in this type of operation is sufficiently high to suspend the catalyst particles in a fairly random movement.
  • the technique of causing random movement of particulate material by the upward flow of the liquid has been identified with the prior art as ebullition.
  • the demetalation of the feed may also be accomplished in a dense fluid bed of solid particulate material, a moving bed operation, or other convenient means for effecting demetalation where the solid particulate material can be replaced as required after becoming spent.
  • the liquid hydrocarbon leaves the upper portion of the demetalation reactor through line 20.
  • Hydrogen gas is purged from the upper portion of the demetalation reactor through line 21. A portion of this gas may be recycled to the demetalation reactor through line 22 provided with pump 23 and connected to line 12.
  • Make-up hydrogen can be provided through line 24, also connected to line 12, if make-up hydrogen gas is required.
  • the hydrocarbon may contain catalyst fines and a fines separator 25 is provided.
  • the fines separator may be a cyclone separator, filter arrangement, or any other convenient means for separating the entrained fines from the withdrawn liquid materiaL'Liquid material is withdrawn from the fines separator through line 30 provided with pump 31 and passed on for further processing. If desired, inter mediate fractionation, not shown, can be provided.
  • Spent fines having relatively high concentrations of deposited metals therein of nickel, vanadium, copper and iron, may be withdrawn from the lower portion of the demetalation reactor through line 32.
  • Demetalation in the reactor will be carried out under the conditions previously mentioned, i.e., temperature within the range of from about 650 F. to 850 F., a pressure within the range of to 3,000 psig, and a space velocity within the range of 0.2 to about 4. Some desulfurization of the charge will also be accomplished during demetalation but will be less effective than desired to be accomplished in the second step of the process.
  • the hydrocarbon charge recovered from the demetalation reactor, and in which the metals level has been significantly reduced, is then subjected to catalytic hydrodesulfurization.
  • the hydrocarbon charge is passed tofurnace 33 and thence through lines 34 and 35 to desulfurization reactor 36.
  • Hydrogen make-up is provided through line 40.
  • Catalytic hydrodesulfurization of sulfur-bearing hydrocarbon charge material has been known and practiced in the petroleum refining art for years. Generally speaking, satisfactory desulfurization results are obtained when operating at a temperature in the range of from about 650F. to about 850 F. and a pressure in the range of about 500 to about 3,000 psig when employing a space velocity in the range of about 3. Suitable catalysts have already been described above.
  • the desulfurization zone comprises a fixed catalyst bed through which the hydrocarbon charge is passed downwardly under desulfurizing conditions.
  • Other types of desulfurization contact zones may be employed such as the trickle process or an ebullating bed of catalyst.
  • the hydrocarbon charge, in admixture with hydrogen rich gas in suitable proportions is caused to through line 43.
  • This gasiform stream may be treated to produce a hydrogen rich stream by any one of a number of known techniques and the thus produced hydrogen rich stream recycled through line 35 for admixture with the hydrocarbon charge to be desulfurized.
  • the remainder of the gasiform stream is purged from the system through line 45.
  • Desulfurized product is removed from the separator through line 46.
  • Metals content of a catalytic cracking stock is often expressed in terms of a metals factor which is defined as parts per million (ppm) Fe 1+ ppm V 10 times the ppm Ni 10 times the ppm Cu. in general, for satisfactory performance of a catalytic cracking unit, the metals factor of the feed stock should be limited to about 5.
  • the invention allows the use of a process complex which includes demetalation which removes, for example, 90 percent of the metals, thus the metals fac- 'tor of the feed stock to this catalytic processing complex can now be as high as 50. This in turn will significantly increase the percentage of crude which provides an acceptable feed stock for catalytic cracking.
  • This processing combination is accomplished by distillation separation of a charge stock into a lighter and a heavier metals rich portion, demetalation of the heavier portion, and feeding the demetalized effluent to the catalytic cracking unit; all or part of the lighter portion would preferably be fed to the same catalytic cracking unit.
  • the hydrocarbon charge stock i.e., crude oil
  • the hydrocarbon charge stock is brought into an. atmospheric pressure still 50 through line 51.
  • Light gases are removed from the still through line 52 while the fraction boiling between the light gases and 400 F. is removed through line 53.
  • the 400-600 F. material from this still is used for catalytic cracking and is passed through lines 54 and 55 to catalytic cracking unit 60.
  • the bottoms from the atmospheric still are passed through line 61 on to a vacuum still 62.
  • the overhead from the vacuum still is passed through line 63 along with hydrogen to a demetalation reactor 64, while the bottoms will generally be passed through line 65 to thermal processing.
  • the effluent from the demetalation reactor is then passed on to the catalytic cracking unit through line 55.
  • the cut temperature of the vacuum still depends on the specific crude oil and Y the efficiency of the demetalation reactor, and is adjusted to yield an effluent from the demetalation reactor having a metals factor nogreater than about 5.
  • the vacuum tower can be completely circumvented and the bottoms from the atmospheric still passed directly to a the demetalation unit.
  • the demetalation reactor 64 of FIG. 4 could be replaced by a complex consisting of both a demetalation reactor and a hydrogenation reactor (not shown).
  • the system of demetalation plus desulfurization and/or denitrogenation, described in more detail in FIG. 3, could be used.
  • the demetalation reactor now permits an increase in the cut temperature of the vacuum still or possibly direct use of the bottoms with an increase in the amount of catalytic cracking feed stock.
  • the hydrogenation reactor increases the hydrogen content of the feed stock leading to greater gasoline production from a given amount of feed stock.
  • either increasing the cut temperature or completely bypassing the vacuum still would increase the amount of metals reaching the hydrogenation catalyst and would significantly curtail the life of this more expensive catalyst.
  • EXAMPLE 1 This example will illustrate the catalytic effect of manganese nodules on demetalation of a topped crude charge stock.
  • the charge stock was Agha .lari topped
  • the manganese nodules were obtained from the bottom of Sturgeon Bay in Lake Michigan. These nodules, after recovery from the lake bottom, were washed to remove salt, water, and mud. They were then crushed, leached with boiling water five times, dried to constant weight at C., and sieved to 14-30 mesh (U.S. Standard Sieve Series).
  • the nodules had the following physical characteristics and chemical composition:
  • EXAMPLE 2 In this example, the effect of sulfiding the manganese nodules is demonstrated.
  • the charge stock and the nodules were the same as those used in Example 1. However, after loading the nodules into the reactor, the nodules were sulfided by passing through the reactor 100 percent hydrogen sulfide at 320 F., at' 1 atmosphere pressure, and at a space velocity of 480 volumes of hydrogen sulfide per volume of nodules for a period of 8 hours. The topped crude oil and hydrogen were passed through the reactor for a period of 10 days. Reaction conditions and results are given in Table II.
  • Example 2 The procedure set forth above in Example 2 was continued for an additional period of 6.9 days. However, during this additional period, the temperatures employed were 800 and 850 F. The reaction conditions and results are given in Table III. In Table III, the hydrogen consumption is given only for the period that the reaction was carried out at 800 F. During the period at which the reaction was carried out at 850 F difficulty was encountered in obtaining measurement of hydrogen consumption.
  • EXAMPLE 6 v This example will illustrate the catalytic effect of manganese nodules on the demetalation of petroleum res1dual oil.
  • the petroleum res1dual oil was a Kuwait atmospheric residual oil and had the following characteristics:
  • Example 1 The nodules were the same as those employed in Example 1 except that they were sieved to 10-20 mesh and were sulfided. Sulfiding was effected by loading the nodules into an upflow reactor and passing hydrogen the same'conditions as set forth in Example 2. Reaction conditions and results are given in Table VI.
  • Example 1 111 SULFURlZATlON CCR REDUCTION DEMETALATION crude oil.
  • the nodules were the same as those em- 45 sulfide through them. Sulfiding was carried out under ployed in Example 1 except that they were sieved to 10-20 mesh. The nodules were packed into a downflow trickle-bed reactor and sulfided as described in Example 1. The charge stock was a Kuwait topped crude and had the following characteristics:
  • EXAMPLE 7 This example will illustrate the results obtained employing a conventional catalyst for demetalation of the same residual oil employed in Example 6.
  • the catalyst employed was a molybdenum oxide-aluminum oxide catalyst and comprised 11.1 weight percent of M00,
  • Example 7 the hydrogen consumption in Example 7 was 563 SCF/B as compared to the lower hydrogen consumption in Example 6 of 222 SCF/B.
  • the table indicates that the extent of demetalation employing the nodules was 53.9 percent. However, it wasconsidered that this was not a representative figure since, on opening the reactor, it was discovered that about half of the catalyst charge had been removed from the reactor by the oil and hydrogen passed through it.
  • the table also indicates that the extent of demetalation employing Catalyst III was 92.5 percent. However, the table also indicates that, while the nodules took out over one-half the metal removed by Catalyst III, the hydrogen consumption with the nodules was less than one-fourth that of Catalyst [11. Further, the table shows that the nodules are far superior to Catalyst I which contains no metal or metal oxide component generally considered to have hydrogenation activity and comparable to Catalyst 11. The table also shows that the hydrogen consumption with the nodules is significantly less than Catalyst 1 and less than one-half that of Catalyst 11.
  • EXAMPLE 9 This example will illustrate the demetalation of a topped petroleum crude oil at relatively low pressures of hydrogen. A relatively high space velocity also was employed.
  • the manganese nodules were the same as those employed in Example 2 and the topped petroleumcrude oil was the same as that employed in Example 1.
  • the reaction conditions and the results obtained are given in Table 1X.
  • the percent demetalation varied between 43.7 and 78.3 percent over the course of the run.
  • the manganese nodules and the topped petroleum crude oil were the same as those in the previous example. During the run, the temperature was increased from 750 F. to 800 F. The reaction conditions and the results obtained are shown in Table X.
  • the percent demetalation varied between 93.1 and 59.2 percent over the course of the run.
  • the nodules employed were obtained from the Blake Plateau in the Atlantic Ocean. These nodules, after crushing and washing with hot water, had the following physical properties and chemical composition:
  • the topped petroleum crude oil was the same as that employed in Example 1.
  • the reaction conditions an results obtained are given in Table X1.
  • the demetalation varied between 95.8 and 79.7 percent over the course of the run.
  • the demetalation varied between 60.1 and 86.1 percent over the course of the run.
  • benzene and hydrogen were passed over three different catalysts packed into a reactor.
  • the first two catalysts were Atlantic Ocean nodules having the physical characteristics and chemical composition as given in Example 8, and Lake Michigan nodules having the physical properties and chemical composition given in Example 1.
  • the third catalyst was the same type of conventional catalyst containing CoO/MoO employed in Example 7.
  • the reaction conditions were as follows:
  • reaction conditions were:
  • EXAMPLE 14 This example will illustrate the processing sequence, described in connection with FIG. 3, of demetalation followed by hydroprocessing for sulfur and nitrogen removal.
  • the Kuwait atmospheric residual oil described in Example 6 is fed to the demetalation reactor 14.
  • the catalyst in the demetalation reactor is manganese nodules which have been crushed to small particle size.
  • the ebullating bed demetalation reactor is operated at 800 F., a Ll-ISV of 1.0, a pressure of 2,000 psig, and a hydrogen circulation rate of 10,000 SCF/B. Ten percent of the catalyst in the demetalation reactor is withdrawn daily and an equivalent amount of fresh catalyst added daily.
  • the metals content of the liquid product from the demetalation reactor is significantly reduced relative to that of the feed to the demetalation reactor.
  • the sulfur content is also reduced but to a lesser extent.
  • the product from the demetalation reactor is passed on to the desulfurization reactor 36.
  • the catalyst in the desulfurization reactor is cobalt molybdate on alumina.
  • the desulfurization reactor is operated at a LI-ISV of 1.0, a temperature of 800 F., a pressure of 2,000 psig and a hydrogen circulation rate of 10,000 SCF/B.
  • the sulfur content of the product from the desulfurization reactor is significantly reduced relative to the feed to the desulfurization reactor.
  • EXAMPLE 15 This example will illustrate the processing sequence, described above in connection with FIG. 4, of demetalation prior to catalytic cracking.
  • a Kuwait crude oil is fed to atmospheric still 50.
  • the bottoms from the atmospheric still which are very similar to the Kuwait atmospheric residual oil described in Example Weight 6, are passed to vacuum still 62.
  • the cut temperature of the vacuum still is adjusted so that the overhead has a metals factor of about 50.
  • This overhead is then passed on to demetalation reactor 64.
  • the catalyst in the demetalation reactor is manganese nodules which have been crushed to small particle size.
  • the ebullating bed demetalation reactor is operated at a LHSV of 0.5, a pressure of 2,000 psig, and a hydrogen circulation rate of 10,000 SCF/B.
  • EXAMPLE 16 This example will illustrate a processing sequence of demetalation and hydrogenation prior to catalytic cracking.
  • a Kuwait crude oil is fed to atmospheric still 50 as illustrated in FIG. 4.
  • the bottoms from the atmospheric still which are very similar to the Kuwait atmospheric residual oil described in Example 6, are passed to vacuum still 62.
  • the cut temperature of the vacuum still is adjusted so that the overhead has a metals factor of about 50.
  • This overhead is then passed on to demetalation reactor 64 containing manganese nodules which have been crushed to small particle size.
  • the ebullating bed demetalation reactor is operated at a temperature of 800 F., a Ll-lSV of 1.0, a pressure of 2,000 psig, and a hydrogen circulation rate of 10,000 SCF/B.
  • Ten percent of the catalyst in the demetalation reactor is withdrawn daily and an equivalent of fresh catalyst added daily.
  • the product from the demetalation reactor which has been significantly reduced in metals content relative to the feed to the demetalation reactor, is passed on to a hydrogenation reactor, i.e., the desulfurization reactor 36 illustrated in FIG. 3.
  • the catalyst in the hydrogenation reactor is cobalt molybdate on alumina.
  • the hydrogenation reactor is operated at a LHSV of 1.0, a temperature of 700 F., a pressure of 2,000 psig, and a hydrogen circulation rate of 7,500 SCF/B.
  • the hydrogen content of the liquid effluent from the hydrogenation reactor is significantly increased relative to the feed to the hydrogenation reactor. This effluent is then passed on to the catalytic cracking unit 60.
  • a process for the demetalation of a hydrocarbon charge stock containing metal impurities comprising contacting said hydrocarbon charge stock with hydrogen and with a catalyst comprising the naturallyoccurring, underwater deposit known as manganese 3.
  • a catalyst comprising the naturallyoccurring, underwater deposit known as manganese 3.
  • said at least a porfrom said manganese nodule by leaching said manganese nodule with an aqueous solution of acid.
  • a process which comprises demetalizing a hydrocarbon charge stock containing metal impurities by contacting said hydrocarbon charge stock with hydrogen and with a catalyst comprising the naturallyoccurring, underwater deposit known as manganese nodules and desulfurizing the demetallized hydrocarbon charge stock by contacting said demetallized hydrocarbon charge stock with hydrogen and with a desulfurizing catalyst under hydrodesulfurizing conditions.

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US4045331A (en) * 1975-10-23 1977-08-30 Union Oil Company Of California Demetallization and desulfurization of petroleum feed-stocks with manganese on alumina catalysts
US4329221A (en) * 1980-09-12 1982-05-11 Mobil Oil Corporation Upgrading of hydrocarbon feedstock
US4338288A (en) * 1978-09-14 1982-07-06 Mobil Oil Corporation Sorbent for removing metals from fluids
US4486298A (en) * 1981-05-28 1984-12-04 Mobil Oil Corporation Adsorptive demetalation of heavy petroleum residua
US4508616A (en) * 1983-08-23 1985-04-02 Intevep, S.A. Hydrocracking with treated bauxite or laterite
US4511458A (en) * 1982-12-30 1985-04-16 Institut Francais Du Petrole Heavy oil process with hydrodemetallation, hydrovisbreaking and hydrodesulfuration
US4546093A (en) * 1984-07-05 1985-10-08 China Petrochemical Development Corp. Preparation of catalyst system for the synthesis of 2-6-xylenol
US4696733A (en) * 1984-09-17 1987-09-29 Mobil Oil Corporation Process for selectively hydrogenating polycondensed aromatics
US5176820A (en) * 1991-01-22 1993-01-05 Phillips Petroleum Company Multi-stage hydrotreating process and apparatus
US5417846A (en) * 1990-03-29 1995-05-23 Institut Francais Du Petrole Hydrotreatment method for a petroleum residue or heavy oil with a view to refining them and converting them to lighter fractions
US20030229583A1 (en) * 2001-02-15 2003-12-11 Sandra Cotten Methods of coordinating products and service demonstrations
US20050133414A1 (en) * 2003-12-19 2005-06-23 Bhan Opinder K. Systems, methods, and catalysts for producing a crude product
US20050133406A1 (en) * 2003-12-19 2005-06-23 Wellington Scott L. Systems and methods of producing a crude product
US20060006556A1 (en) * 2004-07-08 2006-01-12 Chen Hung Y Gas supply device by gasifying burnable liquid
US20060231457A1 (en) * 2005-04-11 2006-10-19 Bhan Opinder K Systems, methods, and catalysts for producing a crude product
US20060234877A1 (en) * 2005-04-11 2006-10-19 Bhan Opinder K Systems, methods, and catalysts for producing a crude product
US20060231456A1 (en) * 2005-04-11 2006-10-19 Bhan Opinder K Systems, methods, and catalysts for producing a crude product
US20060249430A1 (en) * 2005-04-06 2006-11-09 Mesters Carolus Matthias A M Process for reducing the total acid number (TAN) of a liquid hydrocarbonaceous feedstock
US20060289340A1 (en) * 2003-12-19 2006-12-28 Brownscombe Thomas F Methods for producing a total product in the presence of sulfur
US20070000811A1 (en) * 2003-12-19 2007-01-04 Bhan Opinder K Method and catalyst for producing a crude product with minimal hydrogen uptake
US20070000808A1 (en) * 2003-12-19 2007-01-04 Bhan Opinder K Method and catalyst for producing a crude product having selected properties
US20070000810A1 (en) * 2003-12-19 2007-01-04 Bhan Opinder K Method for producing a crude product with reduced tan
US20070012595A1 (en) * 2003-12-19 2007-01-18 Brownscombe Thomas F Methods for producing a total product in the presence of sulfur
US20070295645A1 (en) * 2006-06-22 2007-12-27 Brownscombe Thomas F Methods for producing a crude product from selected feed
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US4045331A (en) * 1975-10-23 1977-08-30 Union Oil Company Of California Demetallization and desulfurization of petroleum feed-stocks with manganese on alumina catalysts
US4338288A (en) * 1978-09-14 1982-07-06 Mobil Oil Corporation Sorbent for removing metals from fluids
US4329221A (en) * 1980-09-12 1982-05-11 Mobil Oil Corporation Upgrading of hydrocarbon feedstock
US4486298A (en) * 1981-05-28 1984-12-04 Mobil Oil Corporation Adsorptive demetalation of heavy petroleum residua
US4511458A (en) * 1982-12-30 1985-04-16 Institut Francais Du Petrole Heavy oil process with hydrodemetallation, hydrovisbreaking and hydrodesulfuration
US4508616A (en) * 1983-08-23 1985-04-02 Intevep, S.A. Hydrocracking with treated bauxite or laterite
US4546093A (en) * 1984-07-05 1985-10-08 China Petrochemical Development Corp. Preparation of catalyst system for the synthesis of 2-6-xylenol
US4696733A (en) * 1984-09-17 1987-09-29 Mobil Oil Corporation Process for selectively hydrogenating polycondensed aromatics
US5417846A (en) * 1990-03-29 1995-05-23 Institut Francais Du Petrole Hydrotreatment method for a petroleum residue or heavy oil with a view to refining them and converting them to lighter fractions
US5176820A (en) * 1991-01-22 1993-01-05 Phillips Petroleum Company Multi-stage hydrotreating process and apparatus
US20030229583A1 (en) * 2001-02-15 2003-12-11 Sandra Cotten Methods of coordinating products and service demonstrations
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GB1347337A (en) 1974-02-27
CA967499A (en) 1975-05-13
DE2158296A1 (de) 1972-07-13
FR2119037A1 (enrdf_load_stackoverflow) 1972-08-04
NL170432C (nl) 1982-11-01
NL7117537A (enrdf_load_stackoverflow) 1972-06-27
FR2119037B1 (enrdf_load_stackoverflow) 1974-06-07
DE2158296C2 (de) 1983-04-21
JPS543481B1 (enrdf_load_stackoverflow) 1979-02-23

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