US3714031A - Residual oil - Google Patents

Residual oil Download PDF

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US3714031A
US3714031A US00090502A US3714031DA US3714031A US 3714031 A US3714031 A US 3714031A US 00090502 A US00090502 A US 00090502A US 3714031D A US3714031D A US 3714031DA US 3714031 A US3714031 A US 3714031A
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percent
catalyst
product
sulfur
oil
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Klinken J Van
Der Toorn L Van
J Ouwerkerk
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Shell USA Inc
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Shell Oil Co
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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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0207—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly horizontal
    • B01J8/0214—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly horizontal in a cylindrical annular shaped bed
    • 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

Definitions

  • the present invention relates to a process for the catalytic hydrodesulfurization of a sulfur-containing hydrocarbon oil or oil fraction. It particularly relates to a process in which a residual oil feedstock is hydrodesulfurized substantially in the liquid phase over a fixed catalyst.
  • Asphaltenes are particularly objectionable in the process asthey are high-molecular weight, non-distillable oil compounds comprising sulfur, nitrogen and/or oxygen and formoil-insoluble coke precursors.
  • Asphaltenes are generally colloidally dispersed within the petroleum crude oil or oil fraction and when subjected to high temperatures have the tendency to flocculate and to deposit on the catalyst particles. Flocculation is favored at the high conversion temperatures applied during hydrodesulfurization conditions since the aromaticity of the liquid phase in which the said asphaltenes are colloidally dispersed is I reduced by hydrogenation and hydrocracking of the (poly)aromatic compounds.
  • ganometallic complexes such as metallo-porphyrins.
  • a considerable quantity of the organometallic complexes are associated with the asphaltenes and thus become concentrated in the residual fraction.
  • the primary difficulty in hydrodesulfurizing crude oils and/or heavy oil fractions is the deposition of asphaltenes on the catalyst particles as it results in heavy coke formation due to the degradation of the asphaltenic compounds.
  • the simultaneous'deposition of the heavy metals onto the catalyst particles together with coke formation from these asphaltenes interferes with the capability of the catalyst to effect a conversion of, in particular, sulfur'containing compounds.
  • the carbonaceous deposit formed during asphaltene flocculation causes the catalyst particles to become bound together resulting in plugging of the fixed catalyst bed accompanied by a rapidly increasing pressure drop. Coke formation will in the long run also contribute to this pressure drop.
  • the increasing pressure drop requires extra compression power which in practice is often no longer available and finally the pressure drop may become so high that it cannot be overcome.
  • the process then has to be interrupted and the catalyst inventory to be replaced or regenerated, if possible.
  • hydrodesulfurization could be started close to the maximally allowable temperature. In this case, however, as a result of too high catalyst activity, hydrodesulfurization will be too deep and no fuel oil will be produced as a'result of severe hydrocracking. Such a process will moreover be very difficult to control since the hydrogen consumption will notbe con stant as a result of changing desulfurization level as the catalyst deactivates.
  • the present invention concerns a direct hydrodesulfurization process which is carried out substantially in the liquid phase, in the presence of a solid sulfur-resistant catalyst, and in which hydrogen sulfide and/or a hydrogen sulfide precursor is added to the oil in a quantity of at least 0.05 percent w, basis feed, at the beginning of the process, but which quantity is decreased continuously or stepwise in the course of the process to less than 80 percent of the quantity added in the beginning of the process.
  • the process of the invention may also be used for other catalytic hydroconversions of residual hydrocarbon oils such as hydrocraeking, for instance, for the production of HVI lubricating base oils from long or short residues.
  • Hydrogen sulfide and/or the dissolved sulfur compound which easily yields hydrogen sulfide are preferably present in the liquid phase in an amount of and/or corresponding to at least 0.1 percent w and more preferably at least 0.5 percent w of hydrogen sulfide.
  • the quantity of hydrogen sulfide and/or hydrogen sulfide precursor added to the feed is lowered so as to keep the level of hydrodesulfurization essentially constant.
  • the quantity of hydrogen sulfide and/or hydrogen sulfide precursor added to the oil is preferably decreased in the course of the process to a quantity of less than 65 percent and more preferably less than 50 percent of the quantity added at the beginning of the process.
  • the sulfur-compound which is a hydrogen sulfide precursor should be present in the liquid phase in a quantity which is equivalent to the amount of hydrogen sulfide required.
  • Hydrogen sulfide precursors include, e.g., sulfur dioxide, carbon disulfide, and the lower alkyl mercaptans with up to eight carbon atoms in the molecule.
  • the hydrodesulfurization process is more stable and a more constant desulfurization level is obtained. More important, however, is that the catalyst life is considerably prolonged and that the catalyst can tolerate a higher metal lay-down before it loses its hydrodesulfurization activity. Owing to the greatly improved catalyst stability, the sulfur-containing hydrocarbon oil or oil fraction will be hydrodesulfurized at substantially constant reaction conditions and the desulfurized product will consequently show substantially constant quality.
  • the process of the invention is carried out substantially in the liquid phase. This means that during the hydrodesulfurization at least percent v of the residual hydrocarbon oil is present in the liquid phase.
  • the hydrogen sulfide is introduced into the process via a product recycle stream, decreasing the quantity of hydrogen sulfide added to the residual oil feed as the run progresses can very suitably be achieved by removing part of the hydrogen sulfide from the recycle stream, for instance, by partly depressurizing and/or partly stripping said recycle stream and/or by increasing the temperature in the high pressure separator used. If the hydrogen sulfide is introduced into the process via a gas recycle stream, decreasing the quantity of hydrogen sulfide added to the residual oil feed can also very suitably be achieved by decreasing the gas rate used.
  • the hydrodesulfurization is to be performed substantially in the liquid phase no more hydrogen should be used for hydrodesulfurizing than can be dissolved in the liquid hydrocarbon phase at the prevailing reaction conditions, thus preventing the creation of a gas phase.
  • at least part of the desulfurized oil product obtained is recycled for admixture with the residual oil or oil fraction to be desulfurized.
  • the liquid phase is thus composed of the residual oil and part of desulfurized oil product recovered from the hydrodesulfurization and recycled thereto. It is preferred that the oil product is recycled in an amount of at least three volumes of oil product, and more preferably, of from five to 30 volumes of oil product, for each volume of residual oil or oil fraction. For most hydrodesulfurization purposes a recycle ratio of from 5 to 15 will be sufficient.
  • the process is carried out in a fixed-bed operation.
  • Fixed beds with axial or radial flow may be used. If a fixed bed with axial flow is applied, the process may be carried out either in upflow or downflow. If the process is operated completely in the liquid phase, a radial flow reactor is preferred.
  • Relative long on-stream periods or catalysts lives will be obtained according to the present invention by applying a radial flow fixed catalyst bed and using a catalyst particle size which is smaller than is usually employed in trickle flow operation. The actual catalyst lives obtained will depend on the heavy metal and asphaltenes content of the oil processed.
  • measures should be taken that at least 40 percent by volume and more preferably 45 to 50 percent volume of the liquid phase passes through the top half of the catalyst bed.
  • This desired flow may be obtained by using a perforated center pipe in the catalyst bed with a relatively large diameter in comparison to the reactor diameter and/or by applying a special center pipe shape, i.e., narrow at the top and wide at the bottom, and/or by providing more apertures at the top of the said center pipe than at its bottom.
  • the liquid phase may flow radially through the fixed catalyst bed either turned away from or towards the center pipe provided in the bed. 1
  • the hydrogen required for the hydrodesulfurization may be provided as a hydrogen-containing gas stream, such as a reformer off-gas stream, or as substantially pure hydrogen.
  • the hydrogen-containing gases contain at least 60 percent volume of hydrogen.
  • the rate of introduction of such gases or of hydrogen is adjusted to provide the process of the invention with hydrogen in an amount of from 5 to 30 N1 and more preferably of from to N1 per kilogram of total feed.
  • total feed is understood the fresh residual oil feed admixed with the recycled desulfurized oil product.
  • the hydrogen supplied may be introduced via the fresh feed or via the oil product recycle. It is preferred, however, to pass both fresh oil feed and recycle product with hydrogen through a hydrogen saturation zone prior to contacting the admixed feed with the hydrodesulfurization catalyst'This saturation zone is preferably near the entrance of the hydrodesulfurization reactor and may be either inside or outside the reactor. In this zone the hydrogen supplied will completely dissolve in the total feed as defined at the operation conditions. It is preferred to supply enough hydrogen that the total feed is substantially completely saturated at the conditions applied.
  • the oil product recovered in a hydrodesulfurization process is called the (hydro)desulfurized product.
  • the desulfurized product may occasionally show a sulfur content close to zero.
  • the hydrogen sulfide or its precursor compound as defined may be introduced together with the hydrogen required for desulfurization or it may be introduced separately either with the fresh feed or via the oil product-recycle.
  • the hydrogen sulfide is introduced th'roughthe recycled desulfurized oil product proper. It has been found that if prior to depressurizing the desulfurized oil product recovered, part of it is recycled for admixture with the oil or oil fraction to be desulfurized, said recycle oil contains sufficient hydrogen sulfide to provide the residual oil feed with the required quantity of hydrogen sulfide.
  • any of the well-known hydrodesulfurization catalysts may be used in the process of the invention.
  • the sulfur-resistant catalysts comprising one or more metals of Group VIB, VIIB and/or VIII metals, their sulfides and/or oxides deposited on an amorphous refractory inorganic oxide of Group II, III or IV elements or compositions of said inorganic oxides.
  • Suitable examples of catalysts of the preferred type comprisenickel-tungsten, nickel-molybdenum, cobalt-molybdenum, nickel-cobalt-molybdenum on silica, alumina, magnesia, zirconia, thoria, boria or hafnia or compositions of the said inorganic oxides, such as silica-alumina, silica-magnesia, alumina-magnesia and the like.
  • the catalyst mentioned may comprise further additives such as boron phosphate or phosphorus, and/or halogens such as fluorine and chlorine.
  • Boron phosphate may be present in an amount from 10 to 40 percent w basis the total catalyst and more preferably from 15 to 30 percent w, whereas the halogens and phosphorus are used in an amount of less than 10 percent w.
  • the catalyst used preferably contains from 2 to 35 percent w and more preferably from 5 to 25 percent w of total metal.
  • the metals of Group VIII are generally applied in a minor quantity of about 0.1 to 10 percent w and the metals of Group VIB are generally applied in a major quantity, of about 2.5 to 30 percent w, the total amount of metal components preferably being less than 35 percent.
  • the atomic ratio of Group VII and Group VIB metals may vary within wide ranges, a range of from 0.1 to 5 being preferred, however.
  • Particularly suitable catalysts for the purpose of the present invention are a commercially available hydrodesulfurization catalyst comprising 4.1 pbw Co/ 10.3 pbw Mo/IOO pbw A1 0 and another one comprising 3.l pbw Ni/ll.7 pbw M0/2;6 pbw P/l00 pbw A1 0 7
  • carriers of the zeolitic type may be used.
  • Particularly suitable alumino-silicate zeolites are the zeolite having a SiO /Al O molar ratio of at least 3, such as zeolite Y.
  • Aluminosilicate zeolites may be used as such or embedded in an inorganic oxide matrix, such as alumina. Usually the matrix is applied in an amount of from 20-80 percent w of the carrier.
  • the catalyst particle size is preferably below 2.0 mm and more preferably in the range of from 0.4 to 1.5 mm. Particularly favorable results have been obtained with a catalyst sieve fraction of 0.5 to 1.0 mm (35-18 mesh).
  • the reaction conditions used for hydrodesulfurization are conventional for this type of operation and may vary within wide limits depending on the type of feedstock used.
  • the temperature is in the range of from 300 to 475C and more preferably from 385 to 445C and total pressures are of from 30 to 350 kg/cm and more preferably from to 225 kg/cm
  • the weight hourly space velocity may vary between wide ranges and is generally between 0.1 and 10 parts by weight of fresh oil feed per part by volume of catalyst per hour, 0.3 to 5 pbw of fresh oil feed being preferred.
  • the severity of the hydrodesulfurization operation is preferably such that at least 40 percent of desulfurization is obtained and more preferably 50 to percent.
  • the recycled desulfurized product may be combined with the fresh oil feed before or after the oil feed has been heated.
  • the recycled product may also be separately introduced in the hydrogen saturation zone. Whatever operation modification is being used, it is preferred that the product to be recycled is taken from the hydrodesulfurization effluent stream prior to depressurizing that stream as discussed.
  • the residual oil to be hydrodesulfurized can be any sulfur-containing petroleum oil comprising residual material. Partial denitrification will occur simultaneously if nitrogen-containing compounds are present in fixed catalyst bed, a long residue of a Caribbean crude oil was treated with hydrogen in the presence of a commercially available hydrodesulfurization catalyst. Hydrodesulfurization was performed on a pilot plant scale, using a reactor with a catalyst inventory of 1,000 ml. The length of the fixed catalyst bed was about 90 cm. The pilot plant was inter alia provided with means to recirculate liquid desulfurized product to the reactor. The recycled product was combined with fresh feed and the total stream was heated prior to introduction into the top of the reactor. A separate hydrogen saturation zone was provided for outside the reactor. Make-up hydrogen was introduced with the fresh feed.
  • the hydrodesulfurization catalyst used was a Co/Mo/Al O catalyst and had the following composition: 4.9 pbw C and 15.7 pbw M00; per 100 pbw A1 0 (dry basis).
  • the catalyst particle size ranged from 0.5 to 1.0 mm. It was presulfided by means of a hydrogen sulfide-containing gas mixture (10 percent volume of H 5) at a pressure of kg/cm and a gas hourly space velocity of 400 1.1".h and a stepwise increase of the temperature from ambient temperature to 350C. Thereafter the reactor was flushed with hydrogen at a pressure of 50 kg/cm. The pressure was finally increased to 150 kg/cm and the feed to be hydrodesulfurized cut in:
  • the Caribbean crude derived long residue was processed at the following conditions:
  • the hydrodesulfurized product obtained had an average sulfur content of about 0.8 percent w sulfur. After desulfurization of 2.1 tons of feed/kg catalyst rapid catalyst deactivation was observed and the life test was terminated. After depressurizing and cooling the spent catalyst was removed for analysis. Based on fresh catalyst about 22 percent w of vanadium and 2.6 percent w of nickel had been laid down on the catalyst. The sulfur content of the catalyst amounted to 15.6 percent W.
  • the total liquid effluent of the reactor of the pilot plant described in Example 1 was cooled down to 70C by heat exchanging it with hot water. Part of the cooled desulfurized product was recycled before the product was conducted to the high-pressure separator and subsequently depressurized in the low-pressure separator. The recycle product, still being under pressure, was admixed with the pressurized fresh feed comprising fresh hydrogen and after heating the total feed was introduced in the reactor.
  • the hydrodesulfurized product obtained had a constant sulfur content of 1.05 percent w in total liquid product.
  • the catalyst life reached was 3.2 tons of oil feed per kg of catalyst (about 1,050 hours). Based on fresh catalyst about 29 percent w of vanadium, 3 percent w of nickel and 16 percent w of carbon had been laid down on the spent catalyst;
  • the present process is especially advantageous in connection with residual oils comprising at least 20 ppmw vanadium and having a sulfur content of at least l .0 percent w.
  • the feedstock may be a whole crude.
  • the high sulfur components of a crude oil and also of the metallo-organic compounds tend to concentrate in the higher boiling fraction the present process will more commonly be applied to a bottoms fraction of a petroleum crude, i.e., one obtained by topping of the crude or by atmospheric of vacuum distillation of the crude.
  • Typical residues will normally be substantially composed of hydrocarbons and/or one or more hetero-atoms-containing a substantial amount of asphaltic material.
  • the oil feed can be one having an initial boiling point or a percent boiling point somewhat below 360C provided that a substantial proportion, for example, 40 to 50 volume percent or more, of its hydrocarbons boil above 360C
  • the residual oil or oil fraction may be a topped crude, a long residue or a short residue.
  • the oil fractions may be subjected to a feed pretreatment such as deep-flashing, deasphalting, hydrorefining with hydrogen-or hydrogen-containing gas mixtures in the absence of any catalyst or the like this is not required for the present direct desulfurization process.
  • Heavy oil fractions which may be processed according to the invention are black oils, visbreaker effluents, tar sand oils and the like or mixtures of such oil fractions. These oil fractions may also be processed admixed with the residual oils or oil fractions mentioned.
  • the residual oil or oil fraction have an alkali metal and/or alkaline earth metal content of less than 50 ppmw.
  • this alkali metal and/or alkaline earth metal content is in the range of from I to 25 ppmw. If the metals content in the oil or oil fraction to be hydrodesulfurized is above the range indicated, it should preferably be reduced by appropriate treat- 1 ment, such as washing or the like.
  • Saturation zone 11 is provided to ensure that the hydrogen fed to the system is completely dissolved in the feed mixture before the latter comes into contact with the catalyst.
  • the feed which under the prevailing reaction conditions is still in catalyst bed through the apertures provided in catalyst bed support 16 and flows through the bed to the center pipe 13 and into the inner space thereof via the apertures provided in pipe 13.
  • the desulfurized oil leaves the reactor 9 by means of line 17.
  • the desulfurized product which is still at the working pressure is partly taken from the system and partly recycled to the reactor via line 27, hot recycle pump 28 and line 29. As the product recycled is not depressurized it still contains hydrogen sulfide formed during desulfurization and hydrogen not consumed during desulfurization. If desired, the recycled product may be diverted via line 30 to line 6, thus bypassing furnace 5. This may be desirable for temperature control and for cooling down the catalyst bed before catalyst replacement.
  • the desulfurized product diverted via line 18 is first cooled in heat-exchanger 19 and then conducted to high-pressure separator 20.
  • a gaseous phase formed and mainly comprising hydrogen, hydrogen sulfide, ammonia and light gaseous hydrocarbons is vented via line 21 and used and/or treated in a manner known in the art (recycle gas).
  • the liquid phase formed and consisting of desulfurized product is withdrawn from the system by means of lines 22 and 23.
  • Line 23 is provided with a valve 24 which is automatically controlled by means of level controller 25.
  • valve 24 in line 23' is shut and the cooled product recycled via line 26, pump 28 and line 30 to the reactor.
  • the valve provided in line 27 may also be kept closed so that the total liquid product is routed via heat-exchanger 19 and separator 20.
  • Reactor 9 is provided with means to introduce an inert gas like nitrogen or additional hydrogen into the reactor (lines 32 and 31 provided with meter 33). The nitrogen is required for displacing any hydrogen before finally opening the reactor for catalyst replacement.
  • the gaseous phase vented via line 21 may bypass the usual gas scrubber for removing hydrogen sulfide and be directly recycled to reactor 9 for providing the required hydrogen gas make-up together with hydrogen sulfide.
  • Ammonia may be removed in the usual way by washing-with water of either the liquid reactor effluent prior to flashing it in the high pressure separator or of the gaseous phase formed after flashing.
  • P- (peptization) value is determined from P,,IFR,,,,,, in which P, stands for the peptizing power of the oil medium and PR is flocculation ratio of the asphaltenes at infinite dilution.
  • a stable fuel has a P- value above 1.0; for the asphaltenes of the crude used FR,,,,, is 35.
  • EXAMPLE 111 The influence of the hydrogen sulfide content of the recycle desulfurized product on catalyst life and on the metaHay down on the catalyst is further shown in this example.
  • Example 1 The pilot plant experiments with the Caribbean crude-derived long residue of Example 1 having a sulfur content of 2.1 percent w and comprising 212 ppmw of vanadium were continued with a run in which the liquid recycle stream was cooled and depressurized to atmospheric pressure. At the beginning of the run the quantity of hydrogen sulfide in the liquid recycle stream was 0.1 percent w and decreased during the run to 0.06 percent w. For this run a fresh batch of the come/A120 catalyst crushed to 0.5-1 .0 mrnparticles was used. The operating conditions applied were similar to those used in Example 11 but the hydrogen gas rate which was 200 N1 per kg of fresh oil feed.
  • Example IV In order to show the influence of increasing temperature on the product properties, in particular on the viscosity of the desulfurized product obtained, the Caribbean crude-derived long residue of Example 1 was desulfurized at constant sulfur level by raising the temperature stepwise during operation. A life test was run in a bench scale apparatus with a catalyst inventory of ml. The catalyst was the same as used in the previous examples. lts particle size was 05-10 mm and it was presulfided before use.
  • the operating conditions were: temperature: from 380 to 420 C; pressure: 150 kg/cm; WHSV (fresh feed): 2.0 kg.l"h.”; recycle ratio of H S-free, desulfurized product to fresh feed: 10 to l; inlet H gas rate: 250 N1 H lkg fresh feed; sulfur level of total liquid product: 0.9-1 .0 percent w.
  • EXAMPLE V The influence of alkali metal present .in residual oils on the desulfurization activity of the catalyst is shown in the following example.
  • a Middle-East crude-derived long residue was hydrodesulfurized over a fixed bed prepared from a fresh batch of the Co/MolAl O catalyst of Example 1.
  • the average particle size of the catalyst was 0.7 mm.
  • the liquid recycle stream was stripped free of hydrogen sulfide at atmospheric pressure in order to demonstrate only the alkali metal effect.
  • EXAMPLE VI A topped Caribbean crude (96.9 percent yield on crude) having sulfur content of 2.84 percent w, a vanadium content of 393 ppmw and a nickel content of 54 ppmw was hydrodesulfurized in an upflow recycle operation carried out substantially in the liquid phase over a fixed catalyst bed prepared from a fresh batch of the Co/Mo/Al O catalyst of Example 1 (particle size used between 0.4 and 1.5 mm). The catalyst was presulfided.
  • EXAMPLE Vll A Caribbean long residue having a sulfur content of 2.1 percent w was hydrodesulfurize'd substantially in the liquid phase over a fixed catalyst bed of 0.5-1 .0 mm crushed particles of the Co/Mo/Al O: catalyst described in Example I. The catalyst was presulfided. The hydrodesulfurization was carried out in upflow operation with product recycle. In one life test the recycle stream of desulfurized product was stripped free from hydrogen sulfide at atmospheric pressure. In another life test the liquid recycle stream was not depressurized and not stripped free from hydrogen sulfide.
  • the quantity of hydrogen sulfide in the liquid recycle stream amounted to 1.0 percent w at the beginning of the run and was gradually decreased in the course of the run to 0.4 percent w at the end of the run.
  • the decrease in hydrogen sulfide content of the liquid recycle stream was achieved by gradually increasing the exit gas rate from 80 Nl/kg at the beginning of the run to 225 Nl/kg at the end of the run.
  • a process for the catalytic hydrodesulfurization of a sulfur-containing residual hydrocarbon oil carried out substantially in a liquid phase in the presence of dissolved hydrogen and a solid sulfur-resistant catalyst which comprises adding to the feedstock a sulfur compound selected from the group consisting of hydrogen sulfide and a hydrogen sulfide precursor in an amount to provide at least 0.05 percent w of hydrogen sulfide in the liquid phase at the beginning of the process, and decreasing the quantity of sulfur compound added during the course of the process to less than 80 percent of the initial quantity as required to maintain an essentially constant hydrodesulfurization level, and
  • liquid phase is a combined feedstock comprising residual oil and recycled desulfurized oil product in an amount of at least 3 volumes of product for each volume of residual oil, and wherein the quantity of added sulfur compound is decreased in the course of the process to less than 65 percent of that added initially.
  • the residual oil is substantially composed of hydrocarbons and one or more hetero atoms-containing organic carbon compounds boiling above 360C, a substantial amount of asphaltic material, and has a sodium content of less than 50 ppmw; and the hydrodesulfurization is carried out at a temperature in the range of from 300C to 475C, a total pressure of from 30 to 350 kg/cm and a weight hourly space velocity of 0.3 to 5 parts by weight of residual oil per part by volume of catalyst per hour.
  • the process of claim 1 wherein the residual oil feedstock has a sulfur content of at least 1.0 percent w, which is reduced to from 50 to 85 percent w of its initial value in the presence of a fixed-bed catalyst having a particle size from 0.4 to 1.5 mm; from 5 to 15 volumes of desulfurized oil product are recycled for each volume of residual oil feedstock; and wherein the process is carried out at a temperature from 385 to 445C, a total pressure from to 225 kglcm a weight hourly space velocity of 0.3 to 5 parts by weight of fresh oil feed per part by volume of catalyst per hour and a hydrogen gas rate of 15 to 20 Nl hydrogen per kilogram of total feed.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4547285A (en) * 1983-10-24 1985-10-15 Union Oil Company Of California Hydrotreating process wherein sulfur is added to the feedstock to maintain the catalyst in sulfided form
US4980046A (en) * 1989-12-28 1990-12-25 Uop Separation system for hydrotreater effluent having reduced hydrocarbon loss
US5275994A (en) * 1991-06-17 1994-01-04 Texaco Inc. Process for preparing a catalyst for removal of hydroprocessing impurities
WO2001094502A1 (en) * 1999-12-22 2001-12-13 Exxonmobil Research And Engineering Company High temperature depressurization for naphtha mercaptan removal
US6387249B1 (en) * 1999-12-22 2002-05-14 Exxonmobil Research And Engineering Company High temperature depressurization for naphtha mercaptan removal
US20030229583A1 (en) * 2001-02-15 2003-12-11 Sandra Cotten Methods of coordinating products and service demonstrations
US20050133416A1 (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
US20060231456A1 (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
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
US20070000810A1 (en) * 2003-12-19 2007-01-04 Bhan Opinder K Method for producing a crude product with reduced tan
US20070000808A1 (en) * 2003-12-19 2007-01-04 Bhan Opinder K Method and catalyst for producing a crude product having selected properties
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ZA706922B (en) 1971-07-28
GB1324167A (en) 1973-07-18
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FR2067349A1 (ja) 1971-08-20
BE758565A (nl) 1971-05-06

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