WO2003002692A2 - Hydrotraitement de composants pour le melange de raffinerie de carburants de transport - Google Patents

Hydrotraitement de composants pour le melange de raffinerie de carburants de transport Download PDF

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Publication number
WO2003002692A2
WO2003002692A2 PCT/US2002/022050 US0222050W WO03002692A2 WO 2003002692 A2 WO2003002692 A2 WO 2003002692A2 US 0222050 W US0222050 W US 0222050W WO 03002692 A2 WO03002692 A2 WO 03002692A2
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Prior art keywords
sulfur
boiling
hydrogenation
fuel
ppm
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PCT/US2002/022050
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English (en)
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WO2003002692A3 (fr
Inventor
George A. Huff, Jr.
Larry W. Kruse
Ozie S. Owen
Monica Cristina Regalbuto
William H. Gong
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Bp Corporation North America Inc.
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Priority to AU2002332412A priority Critical patent/AU2002332412A1/en
Publication of WO2003002692A2 publication Critical patent/WO2003002692A2/fr
Publication of WO2003002692A3 publication Critical patent/WO2003002692A3/fr

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    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof

Definitions

  • the present invention relates to fuels for transportation which are derived from natural petroleum, particularly processes for the production of components for refinery blending of transportation fuels which are liquid at ambient conditions. More specifically, it relates to integrated processes which include selective hydrogenation of high-boiling hydrogenation feedstock whereby the incorporation of hydrogen into hydrocarbon compounds, sulfur-containing organic compounds, and/or nitrogen- containing organic compounds assists by hydrogenation removal of sulfur and/or nitrogen from components for refinery blending of transportation fuels.
  • the integrated hydrotreating processes of this invention advantageously provide their own source of high-boiling hydrogenation feedstock derived from other refinery units, for example, by fractionation of hydrotreated petroleum distillates.
  • the instant hydrotreating process is very selective, i.e. preferentially compounds in which a sulfur atom is sterically hindered are hydrogenated rather than aromatic hydrocarbons.
  • Products can be used directly as transportation fuels and/or blending components to provide, for example, more suitable components for blending into diesel fuels which are more friendly to the environment.
  • Crude oil seldom is used in the form produced at the well, but is converted in oil refineries into a wide range of fuels and petrochemical feedstocks.
  • fuels for transportation are produced by processing and blending of distilled fractions from the crude to meet the particular end use specifications. Because most of the crudes available today in large quantity are high in sulfur, the distilled fractions must be desulfurized to yield products which meet performance specifications and/or environmental standards. Sulfur containing organic compounds in fuels continue to be a major source of environmental pollution. During combustion they are converted to sulfur oxides which, in turn, give rise to sulfur oxyacids and, also, contribute to particulate emissions.
  • Distilled fractions used for fuel or a blending component of fuel for use in compression ignition internal combustion engines are middle distillates that usually contain from about 1 to 3 percent by weight sulfur.
  • Diesel engines are middle distillates that usually contain from about 1 to 3 percent by weight sulfur.
  • a typical specifications for Diesel fuel was a maximum of 0.5 percent by weight.
  • By 1993 legislation in Europe and United States limited sulfur in Diesel fuel to 0.3 weight percent.
  • maximum sulfur in Diesel fuel was reduced to no more than 0.05 weight percent. This world-wide trend must be expected to continue to even lower levels for sulfur.
  • HDS hydrodesulfurization
  • Patent Number 2,912,313 states that an increase in cetane number is obtained by adding both a peroxide and a dihalo compound to middle distillate fuels.
  • U.S. Patent Number 2,472,152 describes a method for improving the cetane number of middle distillate fractions by the oxidation of saturated cyclic hydrocarbon or naphthenic hydrocarbons in such fractions to form naphthenic peroxides.
  • This patent suggests that the oxidation may be accelerated in the presence of an oil-soluble metal salt as an initiator, but is preferably carried out in the presence of an inorganic base.
  • the naphthenic peroxides formed are deleterious gum initiators. Consequently, gum inhibitors such as phenols, cresols and cresyic acids must be added to the oxidized material to reduce or prevent gum formation. These latter compounds are toxic and carcinogenic.
  • U.S. Patent Number 4,494,961 in the name of Chaya Venkat and Dennnis E. Walsh relates to improving the cetane number of raw, untreated, highly aromatic, middle distillate fractions having a low hydrogen content by contacting the fraction at a temperature of from 50° C. to 350° C. and under mild oxidizing conditions in the presence of a catalyst which is either (i) an alkaline earth metal permanganate, (ii) an oxide of a metal of Groups IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIIIB of the periodic table, or a mixture of (i) and (ii).
  • a catalyst which is either (i) an alkaline earth metal permanganate, (ii) an oxide of a metal of Groups IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIIIB of the periodic table, or a mixture of (i) and (ii).
  • European Patent Application 0 252 606 A2 also relates to improving the cetane rating of a middle distillate fuel fraction which may be hydro-refined by contacting the fraction with oxygen or oxidant, in the presence of catalytic metals such as tin, antimony, lead, bismuth and transition metals of Groups IB, IIB, VB, VIB, VIIB and VIIIB of the periodic table, preferably as an oil-soluble metal salt.
  • catalytic metals such as tin, antimony, lead, bismuth and transition metals of Groups IB, IIB, VB, VIB, VIIB and VIIIB of the periodic table, preferably as an oil-soluble metal salt.
  • the application states that the catalyst selectively oxidizes benzylic carbon atoms in the fuel to ketones.
  • U.S. Patent Number 5,814,109 in the name of Bruce R. Cook, Paul J. Berlowitz and Robert J. Wittenbrink relates to producing Diesel fuel additive, especially via a Fischer-Tropsch hydrocarbon synthesis process, preferably a non-shifting process.
  • an essentially sulfur free product of these Fischer- Tropsch processes is separated into a high-boiling fraction and a low-boiling fraction, e.g., a fraction boiling below 700° F.
  • the high- boiling of the Fischer-Tropsch reaction product is hydroisomerizied at conditions said to be sufficient to convert the high-boiling fraction to a mixture of paraffins and isoparaffins boiling below 700° F.
  • the light fraction is hydrotreated to remove substantially all of the sulfur therein.
  • the desulfurized light fraction is then blended with one half of the heavy fraction to product a low sulfur distillate fuel, for example 85 percent by weight of desulfurized light fraction and 15 percent by weight of untreated heavy fraction reduced the level of sulfur from 663 ppm to 310 ppm.
  • a low sulfur distillate fuel for example 85 percent by weight of desulfurized light fraction and 15 percent by weight of untreated heavy fraction reduced the level of sulfur from 663 ppm to 310 ppm.
  • this low sulfur level only about 85 percent of the distillate feedstream is recovered as a low sulfur distillate fuel product.
  • An improved process should be carried out advantageously in the liquid phase using a suitable oxygenation- promoting catalyst system, preferably an oxygenation catalyst capable of enhancing the incorporation of oxygen into a mixture of organic compounds and/or assisting by oxidation removal of sulfur or nitrogen from a mixture of organic compounds suitable as blending components for refinery transportation fuels liquid at ambient conditions.
  • a suitable oxygenation- promoting catalyst system preferably an oxygenation catalyst capable of enhancing the incorporation of oxygen into a mixture of organic compounds and/or assisting by oxidation removal of sulfur or nitrogen from a mixture of organic compounds suitable as blending components for refinery transportation fuels liquid at ambient conditions.
  • This invention is directed to overcoming the problems set forth above in order to provide components for refinery blending of transportation fuels friendly to the environment.
  • This invention contemplates the treatment of various type hydrocarbon materials, especially hydrocarbon oils of petroleum origin which contain sulfur.
  • sulfur contents of the oils are in excess of 1 percent. 2 -3 percent
  • this invention provides a process for the production of fuel or blending component of fuels which are liquid at ambient conditions, which process comprises: (a) providing a high-boiling hydrogenation feedstock comprising a mixture of hydrocarbons and sulfur-containing organic compounds, the feedstock consisting essentially of material boiling between about 200° C. and about 425° C.
  • the recovered product contains less than about 15 ppm of sulfur.
  • useful hydrogenation catalysts comprise at least one active metal, selected from the ⁇ -transition elements in the Periodic Table, each incorporated onto an inert support in an amount of from about 0.1 percent to about 30 percent by weight of the total catalyst.
  • active metals include the ⁇ -transition elements in the Periodic Table elements having atomic number in from 21 to 30, 39 to 48, and 72 to 78.
  • this invention provides a process for the production of refinery transportation fuel or blending components for refinery transportation fuel having a sulfur content less than about 15 ppm, which process comprises: (1) hydrotreating a petroleum distillate consisting essentially of material boiling between about 50° C. and about 425° C.
  • the hydrotreating of the petroleum distillate employs at least one bed of hydrogenation catalyst comprising one or more metals selected from the group consisting of cobalt, nickel, molybdenum and tungsten.
  • the contacting the high-boiling feedstock with a gaseous source of dihydrogen employs at least one bed of hydrogenation catalyst comprising one or more metals selected from the group consisting of nickel, molybdenum and tungsten.
  • the treating of recovered liquid employs at least one bed of solid sorbent comprising alumina.
  • this invention provides a process for the producing a refinery transportation fuel or blending components for refinery transportation fuel having a sulfur content less than about 15 ppm, which process comprises: (I) providing a refinery distillate comprising a mixture of hydrocarbons, sulfur- containing and nitrogen-containing organic compounds, the mixture having a sulfur content up to about 25,000 ppm and consisting essentially of material boiling between about 200° C.
  • Useful catalyst for the hydrotreating comprise a component capable to enhance the incorporation of hydrogen into a mixture of organic compounds to thereby form at least hydrogen sulfide, and a catalyst support component.
  • the catalyst support component typically comprises a refractory inorganic oxide such as silica, alumina, or silica-alumina.
  • Refractory inorganic oxides suitable for use in the present invention, preferably have a pore diameter ranging from about 50 to about 200 Angstroms, and more preferably from about 80 to about 150 Angstroms for best results.
  • the catalyst support component comprises a refractory inorganic oxide such as alumina.
  • Hydrotreating of the refinery distillate preferably employs at least one bed of hydrogenation catalyst comprising cobalt and one or more metals selected from the group consisting of nickel, molybdenum and tungsten, each incorporated onto an inert support in an amount of from about 0.1 percent to about 20 percent by weight of the total catalyst.
  • Contacting of the high-boiling feedstock with a gaseous source of dihydrogen preferably employs at least one bed of hydrogenation catalyst comprising nickel and one or more metals selected from the group consisting of, molybdenum and tungsten, each incorporated onto an inert support in an amount of from about 0.1 percent to about 20 percent by weight of the total catalyst.
  • the treating of recovered liquid employs at least one bed of solid sorbent comprising alumina.
  • the process comprises treating at least a portion of the high-boiling liquid with a solid sorbent, an ion exchange resin, and/or a suitable immiscible liquid containing a solvent or a soluble basic chemical compound, to obtain a high-boiling product having a sulfur content less than about 10 ppm.
  • the fuel further comprises blending at least portions of the low-boiling blending component and the high-boiling product to form fuel for use in compression ignition internal combustion engines, and wherein the fuel exhibits a suitable flash point of at least 38° C. as measure by ASTM D93, and contains less than 15 ppm sulfur. In a further aspect of this invention, the fuel exhibits a suitable flash point of at least 49° C.
  • Beneficially processes of the invention further comprise blending at least portions of the low-boiling blending component and the high-boiling liquid to form fuel for use in compression ignition internal combustion engines, and wherein the fuel exhibits a suitable flash point of at least 38° C. as measure by ASTM D93, and contains less than 15 ppm sulfur.
  • This invention is particularly useful towards sulfur-containing organic compounds in the oxidation feedstock which includes compounds in which the sulfur atom is sterically hindered, as for example in multi-ring aromatic sulfur compounds.
  • the sulfur-containing organic compounds include at least sulfides, heteroaromatic sulfides, and/or compounds selected from the group consisting of substituted benzothiophenes and dibenzothiophenes.
  • Hydrogenation catalysts beneficially contain a combination of metals.
  • the hydrogenation catalyst comprises at least two active metals, each incorporated onto a metal oxide support, such as alumina in an amount of from about 0.1 percent to about 20 percent by weight of the total catalyst.
  • the refinery stream consists essentially of material boiling between about 200° C. and about 425° C.
  • the refinery stream consisting essentially of material boiling between about 250° C. and about 400° C, and more preferably boiling between about 275° C. and about 375° C.
  • the treating of the recovered organic phase includes use of at least one solid sorbent comprising alumina.
  • the drawing is a schematic flow diagram depicting a preferred aspect of the present invention for continuous production of components for blending of transportation fuels which are liquid at ambient conditions.
  • Elements of the invention in this schematic flow diagram include hydrotreating a petroleum distillate with a source of dihydrogen (molecular hydrogen), and fractionating the hydrotreated petroleum to provide a low-boiling blending component consisting of a sulfur-lean, mono-aromatic-rich fraction, and a high-boiling oxidation feedstock consisting of a sulfur-rich, mono-aromatic-lean fraction.
  • This high-boiling oxidation feedstock is further treated by a process which comprises reacting the high- boiling oxidation feedstock with a source of hydrogen at hydrogenation conditions in the presence of a hydrogenation catalyst to assist by hydrogenation removal of sulfur and/or nitrogen from the hydrotreated petroleum distillate.
  • Suitable petroleum distillates generally comprise most refinery streams consisting substantially of hydrocarbon compounds which are liquid at ambient conditions.
  • Suitable refinery streams generally have an API gravity ranging from about 10° API to about 100° API, preferably from about 10° API to about 75 or 100° API, and more preferably from about 15° API to about 50° API for best results.
  • These streams include, but are not limited to, fluid catalytic process naphtha, fluid or delayed process naphtha, light virgin naphtha, hydrocracker naphtha, hydrotreating process naphthas, alkylate, isomerate, catalytic reformate, and aromatic derivatives of these streams such benzene, toluene, xylene, and combinations thereof.
  • Catalytic reformate and catalytic cracking process naphthas can often be split into narrower boiling range streams such as light and heavy catalytic naphthas and light and heavy catalytic reformate, which can be specifically customized for use as a feedstock in accordance with the present invention.
  • the preferred streams are light virgin naphtha, catalytic cracking naphthas including light and heavy catalytic cracking unit naphtha, catalytic reformate including light and heavy catalytic reformate and derivatives of such refinery hydrocarbon streams.
  • Suitable refinery distillate steams generally boil in a temperature range from about 50° C. to about 425° C, preferably 150° C. to about 400° C, and more preferably between about 175° C. and about 375° C at atmospheric pressure for best results.
  • These streams include, but are not limited to, virgin light middle distillate, virgin heavy middle distillate, fluid catalytic cracking process light catalytic cycle oil, coker still distillate, hydrocracker distillate, and the collective and individually hydrotreated embodiments of these streams.
  • the preferred streams are the collective and individually hydrotreated embodiments of fluid catalytic cracking process light catalytic cycle oil, coker still distillate, and hydrocracker distillate.
  • distillate steams can be combined for use as a feedstock.
  • performance of the refinery transportation fuel or blending components for refinery transportation fuel obtained from the various alternative feedstocks may be comparable.
  • logistics such as the volume availability of a stream, location of the nearest connection and short term economics may be determinative as to what stream is utilized.
  • sulfur compounds in petroleum fractions are relatively non-polar, heteroaromatic sulfides such as substituted benzothiophenes and dibenzothiophenes.
  • heteroaromatic sulfur compounds could be selectively extracted based on some characteristic attributed only to these heteroaromatics. Even though the sulfur atom in these compounds has two, non-bonding pairs of electrons which would classify them as a Lewis base, this characteristic is still not sufficient for them to be extracted by a Lewis acid.
  • selective extraction of heteroaromatic sulfur compounds to achieve lower levels of sulfur requires greater difference in polarity between the sulfides and the hydrocarbons.
  • Integrated processes of the invention optionally include one or more selective separation steps using solid sorbents.
  • solid sorbents commonly known to the skilled artisan, include activated carbons, activated bauxite, activated clay, activated coke, alumina, and silica gel.
  • the liquid stream containing hydrogenated material is contacted with solid sorbent for a time sufficient to reduce the sulfur content of the hydrocarbon phase.
  • Integrated processes of the invention can include one or more selective separation steps using an immiscible liquid containing a soluble basic chemical compound.
  • the sulfur containing hydrocarbon material is contacted with the solution of chemical base for a time sufficient to reduce the acid content of the hydrocarbon phase, generally from about 1 second to about 24 hours, preferably from 1 minute to 60 minutes.
  • the reaction temperature is generally from about 10° C. to about 230° C, preferably from about 40° C. to about 150° C.
  • the suitable basic compounds include ammonia or any hydroxide, carbonate or bicarbonate of an element selected from Group I, II, and/or III of the periodic table, although calcined dolomitic materials and alkalized aluminas can be used.
  • mixtures of different bases can be utilized.
  • the basic compound is a hydroxide, carbonate or bicarbonate of an element selected from Group I and/or II element. More preferably, the basic compound is selected from the group consisting of sodium, potassium, barium, calcium and magnesium hydroxide, carbonate or bicarbonate.
  • processes of the present invention employ an aqueous solvent containing an alkali metal hydroxide, preferably selected from the group consisting of sodium, potassium, barium, calcium and magnesium hydroxide.
  • pressures up to 100 atmosphere can be used, pressures are generally in a range from about 15 psi to about 500 psi, preferably from about 25 psi to about 400 psi.
  • Useful distillate fractions for hydrogenation in the present invention consists essentially of any one, several, or all refinery streams boiling in a range from about 50° C. to about 425° C, preferably 150° C. to about 400° C, and more preferably between about 175° C. and about 375° C. at atmospheric pressure.
  • the lighter hydrocarbon components in the distillate product are generally more profitably recovered to gasoline and the presence of these lower boiling materials in distillate fuels is often constrained by distillate fuel flash point specifications.
  • the distillate fractions for hydrogenation in the present invention can comprise high and low sulfur virgin distillates derived from high- and low-sulfur crudes, coker distillates, catalytic cracker light and heavy catalytic cycle oils, and distillate boiling range products from hydrocracker and resid hydrotreater facilities.
  • coker distillate and the light and heavy catalytic cycle oils are the most highly aromatic feedstock components, ranging as high as 80 percent by weight.
  • the majority of coker distillate and cycle oil aromatics are present as mono- aromatics and di-aromatics with a smaller portion present as tri- aromatics.
  • Virgin stocks such as high and low sulfur virgin distillates are lower in aromatics content ranging as high as 20 percent by weight aromatics.
  • the aromatics content of a combined hydrogenation facility feedstock will range from about 5 percent by weight to about 80 percent by weight, more typically from about 10 percent by weight to about 70 percent by weight, and most typically from about 20 percent by weight to about 60 percent by weight.
  • Sulfur concentration in distillate fractions for hydrogenation in the present invention is generally a function of the high and low sulfur crude mix, the hydrogenation capacity of a refinery per barrel of crude capacity, and the alternative dispositions of distillate hydrogenation feedstock components.
  • the higher sulfur distillate feedstock components are generally virgin distillates derived from high sulfur crude, coker distillates, and catalytic cycle oils from fluid catalytic cracking units processing relatively higher sulfur feedstocks. These distillate feedstock components can range as high as 2.5 percent by weight elemental sulfur but generally range from about 0.1 percent by weight to about 0.9 percent by weight elemental sulfur.
  • Nitrogen content of distillate fractions for hydrogenation in the present invention is also generally a function of the nitrogen content of the crude oil, the hydrogenation capacity of a refinery per barrel of crude capacity, and the alternative dispositions of distillate hydrogenation feedstock components.
  • the higher nitrogen distillate feedstocks are generally coker distillate and the catalytic cycle oils. These distillate feedstock components can have total nitrogen concentrations ranging as high as 2000 ppm, but generally range from about 5 ppm to about 900 ppm.
  • the catalytic hydrogenation process may be carried out under relatively mild conditions in a fixed, moving fluidized or ebullient bed of catalyst.
  • a fixed bed of catalyst is used under conditions such that relatively long periods elapse before regeneration becomes necessary, for example an average reaction zone temperature of from about 200° C. to about 450° C, preferably from about 250° C. to about 400° C, and most preferably from about 275° C. to about 350° C. for best results, and at a pressure within the range of from about 6 to about 160 atmospheres.
  • a particularly preferred pressure range within which the hydrogenation provides extremely good sulfur removal while minimizing the amount of pressure and hydrogen required for the hydrodesulfurization step are pressures within the range of 20 to 60 atmospheres, more preferably from about 25 to 40 atmospheres.
  • suitable distillate fractions are preferably hydrodesulfurized before being selectively oxidized, and more preferably using a facility capable of providing effluents of at least one low-boiling fraction and one high-boiling fraction.
  • the hydrogenation process useful in the present invention begins with a distillate fraction preheating step.
  • the distillate fraction is preheated in feed/effluent heat exchangers prior to entering a furnace for final preheating to a targeted reaction zone inlet temperature.
  • the distillate fraction can be contacted with a hydrogen stream prior to, during, and/or after preheating.
  • the hydrogen stream can be pure hydrogen or can be in admixture with diluents such as hydrocarbon, carbon monoxide, carbon dioxide, nitrogen, water, sulfur compounds, and the like.
  • the hydrogen stream purity should be at least about 50 percent by volume hydrogen, preferably at least about 65 percent by volume hydrogen, and more preferably at least about 75 percent by volume hydrogen for best results.
  • Hydrogen can be supplied from a hydrogen plant, a catalytic reforming facility or other hydrogen producing process.
  • the reaction zone can consist of one or more fixed bed reactors containing the same or different catalysts.
  • a fixed bed reactor can also comprise a plurality of catalyst beds.
  • the plurality of catalyst beds in a single fixed bed reactor can also comprise the same or different catalysts.
  • interstage cooling consisting of heat transfer devices between fixed bed reactors or between catalyst beds in the same reactor shell, can be employed. At least a portion of the heat generated from the hydrogenation process can often be profitably recovered for use in the hydrogenation process. Where this heat recovery option is not available, cooling may be performed through cooling utilities such as cooling water or air, or through use of a hydrogen quench stream injected directly into the reactors. Two-stage processes can provide reduced temperature exotherm per reactor shell and provide better hydrogenation reactor temperature control.
  • the reaction zone effluent is generally cooled and the effluent stream is directed to a separator device to remove the hydrogen. Some of the recovered hydrogen can be recycled back to the process while some of the hydrogen can be purged to external systems such as plant or refinery fuel.
  • the hydrogen purge rate is often controlled to maintain a minimum hydrogen purity and remove hydrogen sulfide. Recycled hydrogen is generally compressed, supplemented with "make-up" hydrogen, and injected into the process for further hydrogenation.
  • Liquid effluent of the separator device can be processed in a stripper device where light hydrocarbons can be removed and directed to more appropriate hydrocarbon pools.
  • the separator and/or stripper device includes means capable of providing effluents of at least one low-boiling liquid fraction and one high-boiling liquid fraction.
  • Liquid effluent and/or one or more liquid fraction thereof is subsequently treated to incorporate oxygen into the liquid organic compounds therein and/or assist by oxidation removal of sulfur or nitrogen from the liquid products.
  • Liquid products are then generally conveyed to blending facilities for production of finished distillate products.
  • Operating conditions to be used in the hydrogenation process include an average reaction zone temperature of from about 200° C to about 450° C, preferably from about 250° C. to about 400° C., and most preferably from about 275° C. to about 350° C. for best results.
  • the hydrogenation process typically operates at reaction zone pressures ranging from about 400 psig to about 2000 psig, more preferably from about 500 psig to about 1500 psig, and most preferably from about 600 psig to about 1200 psig for best results.
  • Hydrogen circulation rates generally range from about 500 SCF/Bbl to about 20,000 SCF/Bbl, preferably from about 2,000 SCF/Bbl to about 15,000 SCF/Bbl, and most preferably from about 3,000 to about 13,000 SCF/Bbl for best results.
  • Reaction pressures and hydrogen circulation rates below these ranges can result in higher catalyst deactivation rates resulting in less effective desulfurization, denitrogenation, and dearomatization. Excessively high reaction pressures increase energy and equipment costs and provide diminishing marginal benefits.
  • the hydrogenation process typically operates at a liquid hourly space velocity of from about 0.2 hr-1 to about 10.0 hr" 1 , preferably from about 0.5 hr - 1 to about 3.0 hr - 1 , and most preferably from about 1.0 hr" 1 to about 2.0 hr - 1 for best results. Excessively high space velocities will result in reduced overall hydrogenation.
  • a petroleum distillate is passed to hydrotreater where is it hydrotreated in the presence of a hydrotreating catalyst to remove heteroatoms, particularly sulfur and to saturate aromatics.
  • Suitable catalysts for use in hydrotreating the petroleum distillate according to the present invention are any conventional hydrogenation catalyst used in the petroleum and petrochemical industries.
  • a common type of such catalysts are those comprised of at least one active metal each incorporated onto an inert support.
  • least one active metal is a Group VIII metal, more preferrably a metal is selected from the group consisting of cobalt, nickel and iron, and most preferably a metal is selected from the group consisting of cobalt and nickel.
  • Preferred catalysts are those comprised of at least one Group VIII metal and at least one Group VI metal, preferably selected from the group consisting of molybdenum and tungsten.
  • each incorporated onto a high surface area support material such as alumina, silica alumina, and zeolites.
  • the Group VIII metal is typically present in an amount ranging from about 2 percent to about 20 percent, preferably from about 4 percent to about 12 percent based upon the total weight of catalyst.
  • the Group VI metal will typically be present in an amount ranging from about 5 percent to about 50 percent, preferably from about 10 percent to about 40 percent and more preferably from about 20 percent to about 30 percent based upon the total weight of catalyst. It is within the scope of the present invention that more than one type of hydrogenation catalyst be used in the same bed.
  • Suitable support materials used for catalysts according to the present invention include inorganic refractory materials, e.g., alumina, silica, silicon carbide, amorphous and crystalline silica- aluminas, silica magnesias, alumina-magnesias, boria, titania, zirconia and mixtures and co-gels thereof.
  • Preferred support materials for the catalysts include alumina, amorphous silica- alumina, and the crystalline silica-aluminas, particularly those materials classified as clays or zeolites.
  • the most preferred crystalline silica-aluminas are controlled acidity zeolites which are modified by their method of synthesis, for example by the incorporation of acidity moderators, and post- synthesis modifications such as dealumination.
  • heteroaromatic sulfides from a distillate petroleum fraction by hydrotreating would require that the stream be subjected to very severe catalytic hydrogenation in order to convert these compounds into hydrocarbon's and hydrogen sulfide (H2S).
  • H2S hydrogen sulfide
  • a substantially liquid stream of middle distillates from a refinery source 16 is charged through conduit 1 8 into catalytic reactor 20.
  • a gaseous mixture containing dihydrogen (molecular hydrogen) is supplied to catalytic reactor 20 from storage or a refinery source 12 through manifold 1 4 and conduit 15.
  • Catalytic reactor 20 contains one or more fixed bed of the same or different catalyst which have a hydrogenation-promoting action for desulfurization, denitrogenation, and dearomatization of middle distillates.
  • the reactor may be operated in up-flow, down-flow, or counter-current flow of the liquid and gases through the bed.
  • One or more beds of catalyst and subsequent separation and distillation operate together as an integrated hydrotreating and fractionation system.
  • This system separates unreacted dihydrogen, hydrogen sulfide and other non-condensable products of hydrogenation from the effluent stream and the resulting liquid mixture of condensable compounds is fractionated into a low- boiling fraction containing a minor amount of remaining sulfur and a high-boiling fraction containing a major amount of remaining sulfur.
  • Hydrogenated liquids flow from separation drum 24 into distillation column 30 through conduit 26. Gases and condensable vapors from the top of column 30 are transferred through overhead cooler 40 , by means of conduits 34 and 42 , and into overhead drum 44. Separated gases and non-condensed compounds flow from overhead drum 44 to disposal or further recovery (not shown) through conduit 48. A portion of the condensed organic compounds suitable for. reflux is returned from overhead drum 44 to column 30 through conduit 46.
  • the low-boiling fraction having the minor amount of sulfur- containing organic compounds is withdrawn from near the top of column 30 and transferred to fuel blending facility 100 through conduit 32.
  • This light fraction will typically represent that portion of the stream that contains less than about 50 ppm, preferably less than about 35 ppm, more preferably less than about 15 ppm sulfur, and most preferably less than about 5 ppm sulfur. It should be apparent that this low-boiling fraction from the catalytic hydrogenation is a valuable product in itself.
  • oxygenation is defined as any means by which one or more atoms of oxygen is added to a hydrocarbon molecule.
  • a gaseous source of dioxygen such as air or oxygen enriched air.
  • oxygenation is defined as any means by which one or more atoms of oxygen is added to a hydrocarbon molecule.
  • Particularly suitable catalytic oxygenation processes are disclosed in commonly assigned U.S. Patent Application Serial Number (37,248A) and U.S. Patent Application Serial Number (37,248B).
  • a stream containing oxygenated organic compounds is subsequently separated to recover, for example, a fuel or a blending component of fuel and transferred to fuel blending facility
  • conduit 32 b The stream can alternatively be utilized as a source of feed stock for chemical manufacturing.
  • a portion of the high-boiling liquid at the bottom of column 30 is transferred to reboiler 36 through conduit 35 , and a stream from reboiler 36 is returned to distillation column 30 through conduit 37.
  • a mixture of effluents from hydrogenation reactor 60 is transferred into separation drum 64 through conduit 62 .
  • Gaseous compounds, including unreacted dihydrogen, are recycled to hydrogenation reactor 60 from separation drum 64 through conduit 68 and manifold 58.
  • a purge stream of unreacted dihydrogen, hydrogen sulfide and other non-condensed compounds is taken from separation drum 64 through conduit 65 to hydrogen recovery (not shown).
  • steam is supplied to column 70 from refinery source 67 through conduit 72 .
  • Hydrogenated liquids flow from separation drum 64 into distillation column 70 through conduit 66. Gases and condensable vapors from the top of column 70 are transferred through overhead cooler 80 , by means of conduits 74 and 82 , and into overhead drum 84. Separated gases and non-condensed compounds flow from overhead drum 84 to disposal or further recovery (not shown) through conduit 88. A portion of the condensed organic compounds suitable for reflux is returned from overhead drum 84 to column 70 through conduit 86. Other portions of the condensate are beneficially recycled from overhead drum 84 to separation drum 64 and/or transferred to other refinery uses (not shown) through conduit 87. Aqueous condensate is transferred to water treatment (not shown) from separation drum 84 through conduit 85.
  • a portion of the liquid near the bottom of column 70 is withdrawn and transferred to reboiler 76 through conduit 75 , and a stream of vapor from reboiler 76 is returned to distillation column 70 through conduit 77.
  • a crude hydrotreated high- boiling liquid fraction is supplied to vessel 90 through conduit 78 .
  • Vessel 90 contains a bed of solid sorbent which exhibits the ability to retain acidic and/or other polar compounds, to obtain product containing less sulfur and/or less nitrogen than the feedstock to the oxidation.
  • Product is transferred from vessel 90 to fuel blending facility 100 through conduit 92.
  • a system of two or more reactors containing solid sorbent, configured for parallel flow, is used to allow continuous operation while one bed of sorbent is regenerated or replaced.
  • hydrotreated distillate 150 was cut by distillation into four fractions which were collected at temperatures according to the following schedule.
  • Mono-Ar is mono- aromatics.
  • Di-Ar is di-arc >matics.
  • Tri -Ar is tri- aromatics.
  • Mono-Ar is mono-aromatics. Di-Ar is di-aromatics. Tri-Ar is tri- aromatics.
  • Hydrotreated refinery distillate S-25 was partitioned by distillation to provide feedstock for oxidation using hydrogen peroxide and acetic acid.
  • the fraction collected below temperatures of about 300° C. was a sulfur-lean, monoaromatic-rich fraction identified as S-25-B300.
  • Analyses of S-25-B300 determined a sulfur content of 3 ppm, a nitrogen content of 2 ppm, and 36.2 percent mono-aromatics, 1.8 percent di-aromatics, for a total aromatics of 37.9 percent.
  • the fraction collected above temperatures of about 300° C. was a sulfur-rich, monoaromatic- poor fraction identified as S-25-A300.
  • Hydrotreated refinery distillate S-25 was partitioned by distillation to provide feedstock for hydrogenation.
  • the fraction of S-25 collected above temperatures of about 316° C. was a sulfur- rich, monoaromatic-poor fraction identified as S-25-A316.
  • Analyses of S-25-A316 determined a sulfur content of 80 ppm and a nitrogen content of 102 ppm.
  • a hydrotreated refinery distillate identified as S-150 was partitioned by distillation to provide feedstock for hydrogenation.
  • Analyses of S-150 determined a sulfur content of 1 13 ppm and a nitrogen content of 36 ppm.
  • the fraction of S-150 collected above temperatures of about 316° C. was a sulfur-rich, monoaromatic- poor fraction identified as S-150-A316.
  • Analyses of S- 150-A316 determined a sulfur content of 580 ppm and a nitrogen content of
  • S-DF Another hydrotreated refinery distillate identified as S-DF was partitioned by distillation to provide feedstock for hydrogenation.
  • the fraction of S-DF collected below temperatures of about 288° C. was a sulfur-lean, monoaromatic-rich fraction identified as S-DF-B288.
  • the fraction of S-DF collected above temperatures of about 288° C. was a sulfur-rich, monoaromatic- poor fraction identified as S-DF-A288.
  • Analyses of S-DF-A288 determined a sulfur content of 30 ppm.
  • a hydrotreated distillate from another commercial refinery source was identified as W-DDU-1227 and analyzed. Analyses of W-DDU-1227 determined a sulfur content of 417 ppm. Results of distillation according to ASTM D-86 for the hydrotreated distillate are presented in Table III. Hydrotreated distillate W-DDU-1227 was further analyzed by gas chromatograph to identify the boiling point of the sulfur-containing compounds, and these results are presented in Table IV.
  • Percent is based on total weight of the hydrotreated distillate.
  • Percent S is based on total weight of sulfur in the distillate.
  • a feedstock consisting essentially of is defined as at least 95 percent of the feedstock by volume.
  • essentially free of is defined as absolutely except that small variations which have no more than a negligible effect on macroscopic qualities and final outcome are permitted, typically up to about one percent.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne des procédés économiques pour la production de composants pour le mélange de raffinerie de carburants de transport, par l'hydrogénation sélective de composés organiques contenant de l'azote et/ou du soufre, composés contenus dans des mélanges d'hydrocarbures qui sont liquides à température ambiante. Les procédés d'hydrotraitement intégrés de l'invention, sont conçus pour produire avantageusement leur propre source de matière de base d'hydrogénation à point d'ébullition élevé, dérivée, par exemple, par fractionnement de distillats de pétrole hydrotraités. La matière de base d'hydrogénation à point d'ébullition élevé consistant essentiellement en matière bouillant entre environ 200 °C et environ 425 °C et possédant une teneur en soufre pouvant atteindre environ 2 500 ppm, est mise en contact avec une source gazeuse de dihydrogène dans des conditions d'hydrogénation, en présence d'un catalyseur d'hydrogénation possédant la capacité d'accentuer l'incorporation de l'hydrogène dans un ou plusieurs des composés organiques contenant de l'azote et/ou du soufre, si bien qu'un composé comprenant un mélange d'hydrocarbures et d'autres composés organiques et possédant une teneur en soufre inférieure à environ 35 ppm est produit. Avantageusement, tout ou partie du produit est mélangé(e) à une fraction à bas point d'ébullition d'un distillat hydrotraité, de manière qu'un carburant léger possédant une teneur en soufre inférieure à 15 ppm soit produit.
PCT/US2002/022050 2001-02-08 2002-01-17 Hydrotraitement de composants pour le melange de raffinerie de carburants de transport WO2003002692A2 (fr)

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JP4546160B2 (ja) * 2003-06-10 2010-09-15 ハルドール・トプサー・アクチエゼルスカベット 水素化処理法
FR2858980B1 (fr) * 2003-08-19 2006-02-17 Inst Francais Du Petrole Utilisation d'un catalyseur comprenant un support en carburant de silicium b dans un procede d'hydrodesulfuration selective
US7776205B2 (en) * 2004-04-22 2010-08-17 Exxonmobil Research And Engineering Company Process to upgrade hydrocarbonaceous feedstreams
US7780845B2 (en) * 2004-04-22 2010-08-24 Exxonmobil Research And Engineering Company Process to manufacture low sulfur distillates
US10604709B2 (en) 2017-02-12 2020-03-31 Magēmā Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
US20190233741A1 (en) 2017-02-12 2019-08-01 Magēmā Technology, LLC Multi-Stage Process and Device for Reducing Environmental Contaminates in Heavy Marine Fuel Oil
US11788017B2 (en) 2017-02-12 2023-10-17 Magëmã Technology LLC Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil
CN109837127B (zh) * 2019-04-04 2020-12-18 明硕环境科技集团股份有限公司 一种沼气脱硫装置
US11859140B2 (en) * 2022-02-02 2024-01-02 Saudi Arabian Oil Company Integrated hydrotreating and hydrocracking with continuous hydrotreating catalyst regeneration

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US5114562A (en) * 1990-08-03 1992-05-19 Uop Two-stage hydrodesulfurization and hydrogenation process for distillate hydrocarbons
US5292428A (en) * 1989-05-10 1994-03-08 Davy Mckee (London) Ltd. Multi-step hydrodesulphurization process
EP1063275A1 (fr) * 1999-06-25 2000-12-27 Institut Francais Du Petrole Procédé d'hydrotraitement d'un distillat moyen dans deux zones comprenant une zone intermédiaire de stripage
WO2001081507A1 (fr) * 2000-04-20 2001-11-01 Exxonmobil Research And Engineering Company Production de distillats a faible teneur en soufre et en composes aromatiques

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US5292428A (en) * 1989-05-10 1994-03-08 Davy Mckee (London) Ltd. Multi-step hydrodesulphurization process
US5114562A (en) * 1990-08-03 1992-05-19 Uop Two-stage hydrodesulfurization and hydrogenation process for distillate hydrocarbons
EP1063275A1 (fr) * 1999-06-25 2000-12-27 Institut Francais Du Petrole Procédé d'hydrotraitement d'un distillat moyen dans deux zones comprenant une zone intermédiaire de stripage
WO2001081507A1 (fr) * 2000-04-20 2001-11-01 Exxonmobil Research And Engineering Company Production de distillats a faible teneur en soufre et en composes aromatiques

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AU2002332412A1 (en) 2003-03-03
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