EP2099882A1 - Procédé de conversion d'hydrocarbures - Google Patents

Procédé de conversion d'hydrocarbures

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Publication number
EP2099882A1
EP2099882A1 EP07869795A EP07869795A EP2099882A1 EP 2099882 A1 EP2099882 A1 EP 2099882A1 EP 07869795 A EP07869795 A EP 07869795A EP 07869795 A EP07869795 A EP 07869795A EP 2099882 A1 EP2099882 A1 EP 2099882A1
Authority
EP
European Patent Office
Prior art keywords
liquid
hydrogen
phase
reaction zone
zone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP07869795A
Other languages
German (de)
English (en)
Other versions
EP2099882A4 (fr
Inventor
Peter Kokayeff
Laura E. Leonard
Michael R. Smith
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell UOP LLC
Original Assignee
UOP LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by UOP LLC filed Critical UOP LLC
Publication of EP2099882A1 publication Critical patent/EP2099882A1/fr
Publication of EP2099882A4 publication Critical patent/EP2099882A4/fr
Ceased legal-status Critical Current

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Classifications

    • 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
    • C10G45/22—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 with hydrogen dissolved or suspended in the oil
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • 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
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/307—Cetane number, cetane index
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/42—Hydrogen of special source or of special composition
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Definitions

  • the invention relates to a hydrocarbon conversion process for the production of low or ultra low sulfur hydrocarbons.
  • the invention relates to a hydrocarbon conversion process including a liquid-phase reaction zone.
  • a mild hydrocracking unit which often includes a hydrotreating zone and a hydrocracking zone, is one method to produce diesel boiling range hydrocarbons with a reduced level of sulfur.
  • typical mild hydrocracking units generally cannot produce diesel meeting the ultra low sulfur requirements with acceptable cetane numbers.
  • product from a common mild hydrocracking unit still has 100 to 2000 ppm of sulfur and a relatively low cetane number of 30 to 40.
  • Attempts to improve the quality of the effluent from the mild hydrocracking unit are known, but do so at the expense of overtreating the higher boiling components or through additional high pressure vessels. Overtreated higher boiling components are generally not suitable for subsequent fluid catalytic cracking. Additional high pressure vessels require a large capital investment and are more costly to operate.
  • a process is provided to produce an ultra low sulfur hydrocarbon stream or an ultra low sulfur diesel (e.g., less than 10 ppm sulfur) using a two-phase or liquid-phase continuous reaction zone with a hydrotreating catalyst at conditions effective to convert a diesel boiling range distillate to the ultra low sulfur levels and improved cetane numbers.
  • the liquid-phase continuous reaction zone includes at least one, and preferably a plurality, of liquid-phase continuous reactors.
  • the liquid-phase reactors are smaller and operate at less severe conditions than traditional three-phase or gas-phase systems. Therefore, ultra low levels of sulfur (e.g., less than 10 ppm) with improved cetane numbers (greater than 40) can be achieved without overtreating the hydrocarbonaceous streams as would be required in gas-phase systems.
  • the liquid phase reaction zone follows
  • a hydrocarbonaceous feedstock is first reacted in a hydrodesulfurization zone, such as a mild hydrocracking unit, containing at least a hydrodesulfurization catalyst at conditions effective to produce a hydrodesulfurization zone effluent having a reduced concentration of sulfur of 100 to 2000 ppm.
  • the hydrodesulfurization zone includes a hydrotreating zone and a hydrocracking zone.
  • the hydrodesulfurization zone effluent is then separated in a fractionating zone into at least a diesel boiling range distillate, which is a hydrocarbon stream having a mean boiling point of at least 265 0 C (509 0 F) and generally from 149 0 C (300 0 F) to 382°C (720°F), and may also be separated into other fractions.
  • the diesel boiling point fractions may be combined with fractions having other boiling ranges depending on the application.
  • only the diesel boiling range distillate (or any additional fraction added thereto) is processed to achieve the ultra low sulfur levels and improved cetane rather than the entire hydrodesulfuriztion zone effluent.
  • the diesel boiling range distillate is over-saturated with hydrogen and reacted in the liquid-phase continuous reaction zone using a hydrodesulfurization catalyst to produce a liquid-phase effluent having the ultra low sulfur diesel (less than 10 ppm sulfur) with an improved cetane number (about 40 or greater).
  • the diesel boiling range distillate is oversaturated in an amount effective to produce a liquid phase that has a saturated level of hydrogen throughout the reactor as the reaction proceeds.
  • the liquid phase is over saturated by an amount so that additional hydrogen is continuously available from a small gas phase entrained or otherwise associated with the liquid phase to dissolve back into the liquid phase to maintain the substantially constant level of saturation.
  • levels of over saturation are generally achieved by the liquid phase reaction zone being 100 to 1000 percent saturated, and preferably, 100 to 600 percent saturated with hydrogen.
  • the over-saturated liquid phase preferably has a generally constant level of dissolved hydrogen from one end of the reactor zone to the other.
  • Such hydrogen over-saturated liquid phase reactors may be operated at a substantially constant reaction rate to generally provide higher conversions per pass and permits the use of smaller reactor vessels.
  • such conversion and reaction rates allow the liquid-phase reaction zone to operate without a liquid recycle to achieve the desired USLD.
  • the processes described herein require much lower hydrogen demands than traditional gas-phase systems to achieve the ultra low levels of sulfur.
  • the over saturated liquid phase reaction zone uses up to 97 percent less hydrogen than gas phase reactors to achieve ultra low levels of sulfur.
  • a common trickle-bed, gas-phase reactor requires 10,000 SCF/B of hydrogen while the over saturated liquid phase reaction zone generally requires only 300 to 400 SCF/B of hydrogen.
  • the hydrogen can be supplied to the liquid-phase reactors through a slip stream from a make-up hydrogen system and generally avoid the use of costly recycle gas compressors.
  • the processes described herein are particularly useful for hydrocracking a hydrocarbon oil containing hydrocarbons and/or other organic materials to produce a product containing hydrocarbons and/or other organic materials of lower average boiling point and lower average molecular weight having a reduced level of sulfur, and in particular, ultra lower levels of sulfur.
  • the hydrocarbon feedstocks that may be subjected to hydrocracking by the methods of the invention generally include mineral oils and synthetic oils (e.g., shale oil, tar sand products, etc.) and fractions thereof.
  • Illustrative hydrocarbon feedstocks include hydrocarbonaceous streams having components boiling above 288°C (55O 0 F), such as atmospheric gas oils, vacuum gas oils, deasphalted, vacuum, and atmospheric residua, hydrotreated or mildly hydrocracked residual oils, coker distillates, straight run distillates, solvent-deasphalted oils, pyrolysis-derived oils, high boiling synthetic oils, cycle oils, cat cracker distillates, and the like.
  • a preferred hydrocracking feedstock is a vacuum gas oil or other hydrocarbon fraction having at least 50 percent by weight, and usually at least 75 percent by weight, of its components boiling at a temperature above 371 0 C (700 0 F).
  • a typical vacuum gas oil normally has a boiling point range between 315°C (600 0 F) and 565°C (1050 0 F).
  • These hydrocarbonaceous feed stocks may contain from 0.1 to 4 percent sulfur.
  • the selected hydrocarbonaceous feedstock is combined with a hydrogen-rich stream and then introduced into a hydrodesulfurization zone, such as a mild hydrocracking unit, comprising both a hydrotreating zone to remove hetro atoms and a hydrocracking zone to break carbon bond to form saturated hydrocarbons.
  • a hydrodesulfurization zone such as a mild hydrocracking unit, comprising both a hydrotreating zone to remove hetro atoms and a hydrocracking zone to break carbon bond to form saturated hydrocarbons.
  • the feedstock is first introduced into the hydrotreating zone having a hydrotreating catalyst (or a combination of hydrotreating catalysts) and operated at hydrotreating conditions effective to provide a reduction in sulfur levels to 100 to 2000 ppm.
  • hydrotreating refers to a process wherein a hydrogen- containing treat gas is used in the presence of suitable catalysts which are primarily active for the removal of heteroatoms, such as sulfur and nitrogen from the hydrocarbon feedstock.
  • the hydrotreating zone may contain a single or multiple reactor (preferably trickle-bed reactors) and reach reactor may contain one or more reaction zones with the same or different catalysts to convert sulfur and nitrogen to hydrogen disulfide and ammonia.
  • Suitable hydrotreating catalysts for use in the present invention are any known conventional hydrotreating catalysts and include those which are comprised of at least one Group VIII metal (preferably iron, cobalt and nickel, more preferably cobalt and/or nickel) and at least one Group VI metal (preferably molybdenum and tungsten) on a high surface area support material, preferably alumina.
  • Other suitable hydrotreating catalysts include zeolitic catalysts, as well as noble metal catalysts where the noble metal is selected from palladium and platinum.
  • hydrotreating catalyst be used in the same reaction vessel.
  • the Group VIII metal is typically present in an amount ranging from 2 to 20 weight percent, preferably from 4 to 12 weight percent.
  • the Group VI metal will typically be present in an amount ranging from 1 to 25 weight percent, and preferably from 2 to 25 weight percent. While the above describes some exemplary catalysts for hydrotreating, other known hydrotreating and/or hydrodesulfurization catalysts may also be used depending on the particular feedstock and the desired effluent quality.
  • the hydrotreating zone effluent is directly introduced into a hydrocracking zone to form saturated hydrocarbons.
  • the hydrocracking zone may contain one or more beds of the same or different catalyst.
  • hydrocracking refers to a processing zone where a hydrogen-containing treat gas is used in the presence of suitable catalysts that are primarily active for the breaking of carbon bonds to form saturated hydrocarbons.
  • the preferred hydrocracking catalysts utilize amorphous bases or low-level zeolite bases combined with one or more Group VIII or Group VIB metal hydrogenating components.
  • the hydrocracking zone contains a catalyst which comprises, in general, any crystalline zeolite cracking base upon which is deposited a minor proportion of a Group VIII metal hydrogenating component. Additional hydrogenating components may be selected from Group VIB for incorporation with the zeolite base.
  • the zeolite cracking bases are sometimes referred to in the art as molecular sieves and are usually composed of silica, alumina and one or more exchangeable cations such as sodium, magnesium, calcium, rare earth metals, etc. They are further characterized by crystal pores of relatively uniform diameter between 4 and 14 Angstroms (10 "1 meters). It is preferred to employ zeolites having a relatively high silica/alumina mole ratio between 3 and 12.
  • Suitable zeolites found in nature include, for example, mordenite. stilbite, heulandite, ferrierite, dachiardite, chabazite, erionite and faujasite.
  • Suitable synthetic zeolites include, for example, the B, X, Y and L crystal types, e.g., synthetic faujasite and mordenite.
  • the preferred zeolites are those having crystal pore diameters between 8-12 Angstroms (10 " meters), wherein the silica/alumina mole ratio is 4 to 6.
  • a prime example of a zeolite falling in the preferred group is synthetic Y molecular sieve.
  • the natural occurring zeolites are normally found in a sodium form, an alkaline earth metal form, or mixed forms.
  • the synthetic zeolites are nearly always prepared first in the sodium form.
  • Hydrogen or "decationized" Y zeolites of this nature are more particularly described in US 3,130,006 to Rabo et al., which is hereby incorporated herein by reference in its entirety.
  • Mixed polyvalent metal-hydrogen zeolites may be prepared by ion-exchanging first with an ammonium salt, then partially back exchanging with a polyvalent metal salt and then calcining.
  • the hydrogen forms can be prepared by direct acid treatment of the alkali metal zeolites.
  • the preferred cracking bases are those which are at least 10 percent, and preferably at least 20 percent, metal-cation-deficient, based on the initial ion-exchange capacity.
  • a specifically desirable and stable class of zeolites are those wherein at least 20 percent of the ion exchange capacity is satisfied by hydrogen ions.
  • the active metals employed in the preferred hydrocracking catalysts of the present invention as hydrogenation components are those of Group VIII (i.e., iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum). In addition to these metals, other promoters may also be employed in conjunction therewith, including the metals of Group VIB (e.g., molybdenum and tungsten).
  • the amount of hydrogenating metal in the catalyst can vary within wide ranges. Broadly speaking, any amount between 0.05 percent and 30 percent by weight may be used. In the case of the noble metals, it is normally preferred to use 0.05 to 2 weight percent.
  • the preferred method for incorporating the hydrogenating metal is to contact the zeolite base material with an aqueous solution of a suitable compound of the desired metal wherein the metal is present in a cationic form. Following addition of the selected hydrogenating metal or metals, the resulting catalyst powder is then filtered, dried, pelleted with added lubricants, binders or the like if desired, and calcined in air at temperatures of, e.g., 371° to 648°C (about 700° to 1200 0 F) in order to activate the catalyst and decompose ammonium ions.
  • the zeolite component may first be pelleted, followed by the addition of the hydrogenating component and activation by calcining.
  • the foregoing catalysts may be employed in undiluted form, or the powdered zeolite catalyst may be mixed and copelleted with other relatively less active catalysts, diluents or binders such as alumina, silica gel, silica-alumina cogels, activated clays and the like in proportions ranging between 5 and 90 weight percent.
  • diluents may be employed as such or they may contain a minor proportion of an added hydrogenating metal such as a Group VIB and/or Group VIII metal.
  • Additional metal promoted hydrocracking catalysts may also be utilized in the process of the present invention which comprises, for example, aluminophosphate molecular sieves, crystalline chromosilicates and other crystalline silicates. Crystalline chromosilicates are more fully described in US 4,363,718 to Klotz, which is hereby incorporated herein by reference in its entirety.
  • the hydrocracking of the hydrocarbonaceous feedstock in contact with at least a hydrocracking catalyst is conducted in the presence of hydrogen and preferably at hydrocracking reactor conditions effective for saturating the hydrocarbonaceous stream and to effect conversion of the stream to the diesel boiling range distillate (about 149 0 C (300 0 F) to 382 0 C (72O 0 F) and other, lighter products.
  • the hydrocracking zone may operate at a temperature from 232°C (450 0 F) to 482°C (900 0 F), a pressure from 3.5 MPa (500 psig) to 17.3 MPa (2500 psig), a liquid hourly space velocity (LHSV) from 0.1 hr "1 to 30 hr "1 , and a hydrogen circulation rate from 500 (84 normal m 3 /m 3 ) to 10000 (1700 normal m 3 /m 3 ) standard cubic feet per barrel.
  • the resulting effluent from the hydrocracking zone is then introduced into a separation zone.
  • the effluent is first contacted with an aqueous stream to dissolve any ammonium salts and then partially condensed.
  • the stream may then be introduced into a high pressure vapor-liquid separator operating to produce a vaporous hydrocarbonaceous stream boiling in the range from 0 0 C (30 0 F) to 32°C (90 0 F) and a liquid hydrocarbonaceous stream having a reduced concentration of sulfur and boiling in a range greater than the vaporous hydrocarbonaceous stream.
  • the high pressure separator operates at a temperature from 38 0 C (100 0 F) to 200 0 C (400 0 F) and a pressure from 3.5 MPa (500 psig) to 17.3 MPa (2500 psig) to separate such streams.
  • the vapor from the separator is preferably directed to an amine scrubber to remove contaminates, and then through a recycle gas compressor to be recycled back to the make-up hydrogen system and/or the hydrotreating reaction zone.
  • the liquid hydrocarbonaceous stream from the separator is preferably directed to a fractionation zone where the lighter products, such as diesel boiling range hydrocarbons, kerosene and naphtha, are separated from the heavier products, such as a fluid catalytic cracker (FCC) feed stream.
  • FCC fluid catalytic cracker
  • the diesel boiling range hydrocarbons (and any additional selected hydrocarbons), which are preferably separated as a distillate in the fractionation zone, are directed to a liquid-phase reaction zone at conditions effective to ultimately produce an effluent including the ultra low sulfur diesel (i.e., less than 10 ppm sulfur) with improved cetane numbers (i.e., 40 to 60).
  • the ultra low sulfur diesel i.e., less than 10 ppm sulfur
  • cetane numbers i.e., 40 to 60
  • the liquid-phase reaction zone is operated at a temperature from 315°C (600 0 F) to 400 0 C (75O 0 F), a pressure from 2.1 MPa (300 psig) to 13.8 MPa (2000 psig) (preferably 3.5 MPa (500 psig) to 6.2 MPa (9000 psig)), and a liquid hourly space velocity from 0.5 hr "1 to 10 hr "1 to produce the effluent with less than 10 ppm sulfur and cetane numbers from 40 to 60.
  • the liquid-phase reaction zone preferably includes a hydrodesulfurization catalyst, which can be any of the previously described hydrotreating catalysts, in amounts effective to convert the diesel boiling distillate to ULSD with improved cetane numbers.
  • the diesel boiling range distillate (and any other selected distillate fractions) is saturated, and preferably, over-saturated with hydrogen prior to being introduced into one or more liquid-phase continuous reactors in the liquid-phase reaction zone. That is, in such aspect, the liquid-phase reaction zone also has a small vapor phase. In one such aspect, the liquid phase is over-saturated by adding an amount of hydrogen to the distillate stream effective to maintain a substantially constant level of dissolved hydrogen throughout the reaction zone as the reaction proceeds.
  • the reaction proceeds and consumes the dissolved hydrogen, there is sufficient over-saturation to continuously provide additional hydrogen to dissolve back into the liquid phase in order to provide a substantially constant level of dissolved hydrogen (such as generally provided by Henry's law, for example).
  • the liquid phase remains substantially saturated with hydrogen even as the reaction consumes dissolved hydrogen.
  • Such a substantially constant level of dissolved hydrogen is advantageous because it provides a generally constant reaction rate in the liquid-phase reactors.
  • the diesel boiling range distillate or liquid phase is 100 percent to 1000 percent saturated, and, preferably, 100 percent to 600 percent saturated with hydrogen to achieve such levels of over saturation discussed above.
  • the hydrogen will comprise a bubble flow of fine or generally well dispersed gas bubbles rising through the liquid phase in the reactor. In such form, the small bubbles aid in the hydrogen dissolving in the liquid phase.
  • the relative amount of hydrogen required to maintain a liquid-phase continuous system, and the preferred over-saturation thereof is dependent upon the specific composition of the hydrocarbonaceous feedstock, the level or amount of conversion to lower boiling hydrocarbon compounds, the composition and quantity of the lower boiling hydrocarbons, and/or the reaction zone temperature and pressure.
  • the appropriate amount of hydrogen required will depend on the amount necessary to provide a liquid-phase continuous system, and the preferred over-saturation thereof, once all of the above-mentioned variables have been selected.
  • the liquid-phase reaction zone may include a plurality of liquid-phase continuous reactors in either a serial and/or parallel configuration.
  • a serial configuration the effluent from one reactor is the feed to the next reactor, and in a parallel configuration, the feed is split between separate reactors.
  • the feed stream to each reactor would be saturated, and preferably, slightly over-saturated with hydrogen so that each reactor has a constant amount of dissolved hydrogen throughout the reaction zone.
  • the output from the liquid-phase reaction zone is an effluent having the ULSD with improved cetane number.
  • an integrated processing unit 10 includes a hydrodesulfurization zone 12, a fractionation zone 14, and a liquid-phase continuous reaction zone 16 that operate to produce at least an ULSD having less than 10 ppm sulfur and a cetane number of 40 to 60.
  • the hydrodesulfurization zone 12 includes at least a hydrotreating zone 18 including a trickle-bed reactor(s) and a hydrocracking zone 20 including a trickle-bend reactor(s).
  • the fractionation zone 14 includes a distillation column(s).
  • the liquid phase reaction zone 16 includes one or more liquid phase continuous reactor vessels.
  • a feedstream preferably comprising vacuum gas oil is introduced into the integrated process 10 via line 22.
  • a hydrogen-rich gaseous stream is provided via line 24 and joins the feedstream to produce a resulting admixture that is transported via line 26 to the hydrotreating zone 18 to reduce the levels of sulfur to 100 to 2000 ppm.
  • a resulting effluent stream is removed from hydrotreating zone 18 via line 28 and introduced into the hydrocracking zone 20 to provide a diesel boiling range distillate and other lighter products.
  • a resulting effluent stream from the hydrocracking zone 20 is preferably cooled and transported via line 30 into a high pressure separator 32 where a liquid hydrocarbonaceous stream is separated from a vapor or gas stream.
  • the gas stream is removed from the high pressure separator 32 via line 34 and preferably fed to an amine scrubber 36 to remove sulfur components and then to a recycle gas compressor 38 via line 40. Thereafter, a hydrogen rich stream may be added back to the bulk hydrogen in line 24, which is eventually added to the inlet of the hydro treating reaction zone 18. If needed, additional hydrogen may be provided from a make-up hydrogen system via line 41.
  • the liquid stream from the separator 32 is routed via line 42 to the fractionation zone 14 where at least the diesel boiling range distillate is removed therefrom via line 44 and a higher boiling range hydrocarbonaceous stream is removed via line 46.
  • line 46 is introduced into a downstream fluid catalytic cracking unit (not shown).
  • the diesel boiling range distillate is directed in line 44 to the continuous liquid phase reaction zone 16 from the fractionation zone 14.
  • the diesel boiling range distillate is saturated, and most preferably, over-saturated (about 100 to 1000 percent saturation, and preferably 100 to 600 percent saturation) with hydrogen provided by a slip stream 48 from the make-up hydrogen system 41 effective to permit the liquid-phase reaction zone 16 to operate with a substantially constant level of dissolved hydrogen (such as, for example, a hydrogen saturated liquid phase) even as the reactions consume the hydrogen because the over-saturation provides additional hydrogen to continuously re-dissolve back into the liquid phase. That is, for example, the reaction preferably proceeds in the liquid- phase reaction zone without additional sources of hydrogen external to the reactor.
  • the liquid-phase reaction zone 16 includes at least one, and preferably, two liquid-phase continuous reactors 50 connected in a serial arrangement.
  • a liquid-phase effluent from a first liquid-phase reactor 52 is directed via line 54 to a second liquid-phase reactor 56.
  • another hydrogen slip stream 58 from the hydrogen make-up system 41 is combined with line 54 to saturate, and preferably, over- saturate the hydrocarbons in line 54 in a manner similar to that with the first reactor.
  • the resulting effluent from the second reactor 56 is withdrawn as the final product via line 60 and includes the ULSD having the improved cetane rating.
  • liquid-phase reaction zone can include more or less reactors in either serial and/or parallel configurations.

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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

Procédé pour la production d'un gas-oil à teneur en soufre ultra faible avec moins de 10 ppm de soufre, au moyen d'une zone de réaction continue en deux phases ou en phase liquide de manière à convertir un distillat à intervalle de distillation du gas-oil, obtenu, de préférence, à partir d'une unité d'hydrocraquage doux. Selon un mode de réalisation, ce distillat est introduit dans une zone de réaction continue en phase liquide sursaturée avec de l'hydrogène dans une quantité efficace, de manière que la phase liquide reste sensiblement saturée avec l'hydrogène dans la zone de réaction, à mesure que les réactions s'effectuent.
EP20070869795 2006-12-29 2007-12-21 Procédé de conversion d'hydrocarbures Ceased EP2099882A4 (fr)

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US11/618,623 US20080159928A1 (en) 2006-12-29 2006-12-29 Hydrocarbon Conversion Process
PCT/US2007/088628 WO2008083094A1 (fr) 2006-12-29 2007-12-21 Procédé de conversion d'hydrocarbures

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EP2099882A1 true EP2099882A1 (fr) 2009-09-16
EP2099882A4 EP2099882A4 (fr) 2010-11-10

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EP (1) EP2099882A4 (fr)
WO (1) WO2008083094A1 (fr)

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WO2008083094A1 (fr) 2008-07-10
US20080159928A1 (en) 2008-07-03

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