WO2017021987A1 - Système et procédé d'hydroconversion d'huiles lourdes à l'aide de réacteurs à catalyseur dispersé ou avec un lit de catalyseur expansé avec introduction de gaz au niveau de la tête du réacteur - Google Patents

Système et procédé d'hydroconversion d'huiles lourdes à l'aide de réacteurs à catalyseur dispersé ou avec un lit de catalyseur expansé avec introduction de gaz au niveau de la tête du réacteur Download PDF

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WO2017021987A1
WO2017021987A1 PCT/IT2015/000247 IT2015000247W WO2017021987A1 WO 2017021987 A1 WO2017021987 A1 WO 2017021987A1 IT 2015000247 W IT2015000247 W IT 2015000247W WO 2017021987 A1 WO2017021987 A1 WO 2017021987A1
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reactor
gas
catalyst
biphasic
hydroconversion
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PCT/IT2015/000247
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English (en)
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Luigi Patron
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Luigi Patron
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Priority to EP15820648.2A priority Critical patent/EP3331968B1/fr
Publication of WO2017021987A1 publication Critical patent/WO2017021987A1/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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/22—Separation of effluents
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/36—Controlling or regulating
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/26—Controlling or regulating
    • 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
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/06—Vacuum distillation
    • 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
    • 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
    • C10G2300/4081—Recycling aspects

Definitions

  • the present invention relates to heavy oil hydroconversion systems which employ reactors with dispersed catalyst or with expanded catalyst bed (in which also dispersed catalyst is possibly fed or in which only dispersed catalyst is fed). More precisely, the present invention refers to a system of the aforesaid type in which the extraction of the reaction liquid through the biphasic effluent is enhanced by means of the introduction of gas at the head of the reactor, in a zone containing biphasic foam above the reaction liquid.
  • the invention also refers to a method for hydroconversion of heavy oils that can be actuated by means of the aforesaid system.
  • hydrocarbons are present in variable percentage that have a boiling point higher than 540 °C.
  • Such hydrocarbons containing metals such as nickel, vanadium and iron, and heteroatoms such as S, N and O constitute a not-totally-distillable heavy fraction of said oils. If subjected to evaporation, said hydrocarbons in fact produce a quantity of carbon residue (expressed as % CCR, i.e. Conradson Carbon Residue - ASTM D189) that is greater the lower their hydrogen content.
  • the heavy oils are subjected to a temperature treatment with hydrogen and suitable catalysts by means of which the aforesaid heavy fraction (also termed "carbonaceous fraction") is converted into distillable hydrocarbons. Said treatment is also known as “hydroconversion”.
  • the catalysts employed in such treatments are generally defined “hydrogenation” catalysts or “hydroconversion" catalysts.
  • hydroconversion treatment is aimed to obtain products free of carbon residue, which can therefore be fed to subsequent treatments of hydrocracking and hydrotreating, by means of which said products attain quality specifications required by the market or they can be used for other refining processes.
  • the hydrocracking and hydrotreating technologies are well-tested and available on the market, therefore further details thereon will not be provided herein.
  • the hydroconversion treatment can be carried out in pressurized cylindrical vessels (i.e. "reactors") with distribution of the hydrogen at the base, where also the heavy oil to be converted is introduced.
  • the charge stock to be converted and the hydrogen come into contact in the presence of a hydrogenation catalyst (usually comprising molybdenum) dispersed in the reaction liquid or carried on a solid support, structured in small cylinders or microspheres, constituted by silica and/or alumina.
  • the catalyst deposited on a solid support will also be indicated hereinbelow in the present description with the expression "supported catalyst”. If the hydrogenation catalyst is dispersed in the reaction liquid, the reactor in which the hydroconversion treatment is carried out is defined "with dispersed catalyst".
  • the reactor in which the hydroconversion treatment is carried out is defined "with expanded catalyst bed".
  • a third category of hyd reconversion reactors is constituted by reactors with expanded catalyst bed in which dispersed catalyst is also fed.
  • a fourth category of hydroconversion reactors is constituted by reactors with expanded catalyst bed in which only dispersed catalyst is fed.
  • the catalyst can be introduced into the reactor in various modes, such as by means of an oil-soluble precursor (i.e. a metal compound capable of generating the active species when it is in contact with the charge stock and the hydrogen).
  • an oil-soluble precursor i.e. a metal compound capable of generating the active species when it is in contact with the charge stock and the hydrogen.
  • the catalyst of dispersed type also termed “slurry catalyst” remains uniformly and stably dispersed in the reaction liquid from which it can be separated, by way of example, via filtration, centrifugation or settling by decanter.
  • slurry catalyst remains uniformly and stably dispersed in the reaction liquid from which it can be separated, by way of example, via filtration, centrifugation or settling by decanter.
  • the maximum catalytic effect is attained at concentrations of metal in the reaction liquid around 1000 ppm by weight.
  • the dispersed catalyst can be combined with a silica-alumina based compound or a zeolite in order to facilitate the denitrification of the charge stock.
  • a nozzle grid is present at the base of the reactor with dispersed catalyst at the base of the reactor with dispersed catalyst.
  • the commercial application of the hydroconversion systems using reactors with dispersed catalyst has been up to now discouraged owing to the high catalyst consumptions. Being dispersed in the reaction liquid, such catalyst flows out with the latter from the reactor; this involves the need to continuously replenish the reaction liquid with fresh catalyst.
  • the solid elements on which the hydrogenation catalyst is deposited are maintained suspended in the reaction liquid by means of a circulation thereof, obtained by means of a pump inside or outside the reactor.
  • Said pump is also defined “ebullating pump”.
  • the reactors with expanded catalyst bed are also known as “ebullated catalytic bed reactors”.
  • a funnel can be present that is provided with a “downcomer” pipe that collects the liquid in the upper part of the reactor and conveys it downward, being suctioned by the circulation pump.
  • the hydrogen is generally introduced at the base of the reactor at a superficial velocity of several centimeters per second (measured as hydrogen volume at reaction temperature and pressure, fed in the unit of time and divided by the area of the reactor cross section).
  • the introduction of the hydrogen generates a set of bubbles which, by ascending the reaction liquid, induces the remixing and ensures high heat and mass transfer coefficients both in axial direction and in radial direction of the reactor, even in the absence of agitator or mechanical mixing systems.
  • the hydrogen, the volatile conversion products and the reaction liquid generate an effluent (defined "biphasic") which is sent to a gas-liquid separator, from whose head the gaseous phase exits from which - by means of condensation in one or more stages - the volatile conversion products, as well as the residual hydrogen which is sent to the purification section in order to then be reused, are recovered.
  • reaction liquid descends to the bottom of the separator; such reaction liquid is constituted by conversion products (mainly with high boiling point) dissolved in the non-converted fraction of charge stock, and reaction-generated solids comprising the sulfides of the metals present in the charge stock, coke, asphaltene resins that are insoluble and solids due to the catalyst.
  • conversion products mainly with high boiling point
  • reaction-generated solids comprising the sulfides of the metals present in the charge stock, coke, asphaltene resins that are insoluble and solids due to the catalyst.
  • the sum of the weight flow rates of the hydrocarbons extracted at the head of the separator and of the hydrocarbons, with a boiling point up to 540 °C, extractable from the reaction liquid of the separator bottom, can be taken as a measure of the reactor's hydroconversion capacity, whether the reactor is of the type with dispersed catalyst or is of the type with expanded catalyst bed (in which dispersed catalyst is also possibly fed or in which only dispersed catalyst is fed).
  • the conversion products having a low boiling point for example less than 300 °C
  • the conversion products having a higher boiling point tend to be accumulated in the reaction liquid within the reactor and are extracted, both through the gaseous phase and through the liquid phase of the biphasic effluent, to an extent that increases with the superficial velocity of the hydrogen introduced at the base of the reactor.
  • the conversion products having a boiling point comprised between 300 °C and 540 °C are also identified with the adjective "high-boiling".
  • the negative effect of the accumulation of the high-boiling conversion products on the hydroconversion capacity is particularly important in the case of commercial scale reactors where the accumulation advances with the height, progressively reducing the hydroconversion unit capacity of the system (defined as m 3 of charge stock converted in one hour per m 3 of reaction volume). A unit capacity that is thus reduced limits the convenience of making large-height reactors.
  • the accumulation of the high-boiling conversion products in the reaction liquid is a consequence of an extraction mode that is not suitable for the rate with which said conversion products are generated.
  • the object of the present invention is to overcome the aforesaid drawbacks and to indicate an alternative solution to that illustrated in the abovementioned Italian patent 1415850 in order to improve the extraction of the high-boiling conversion products through the biphasic effluent that flows out from the head of the reactor, with a mode applicable both to reactors with dispersed catalyst and to reactors with expanded catalyst bed (in which dispersed catalyst is also possibly fed or in which only dispersed catalyst is fed).
  • the objective of the present invention is to reduce the accumula- tion of high-boiling conversion products in the reactors with dispersed catalyst and in the reactors with expanded catalyst bed (in which dispersed catalyst is also possibly fed or in which only dispersed catalyst is fed) during a heavy oil hydroconversion process.
  • the present invention regards a system for hydroconversion of heavy oils which employs a reactor with dispersed catalyst or with expanded catalyst bed (in which dispersed catalyst is also possibly fed or in which only dispersed catalyst is fed), in which the conversion products are obtained from the biphasic effluent that flows out at the head of the reactor.
  • the hydrogen introduced at the bottom of the reactor generates a set of bubbles that ascend the reaction liquid.
  • the reaction liquid At the surface that delimits the reaction liquid, there is the separation of the bubbles and the consequent degassing of the liquid.
  • the gas bubbles Due to the foaming properties of the heavy oils (a consequence of the presence of heteroatoms with surfactant effect, such as S, N and O, mainly in the fraction with boiling point higher than 540 °C), the gas bubbles, being recombined, produce a flow of biphasic foam that by ascending lifts the reaction liquid towards the head of the reactor where the outlet duct is placed.
  • Charge stocks lacking fractions with boiling point higher than 540 °C do not produce biphasic foam to an extent sufficient for lifting the liquid towards the outlet duct.
  • the quantity (kg) of dispersed (and hence entrained) reaction liquid in one m 3 of biphasic effluent is provided, in a first approximation, by the value of the density (kg/m 3 ) of the biphasic effluent.
  • the density of the biphasic effluent, in the outlet duct of the reactor is several times lower than that of the biphasic foam which, within the reactor, ascends towards the outlet duct. More precisely, the density of the biphasic effluent is for example from 4 to 6 times lower than that of the biphasic foam.
  • reaction liquid present in the biphasic foam falls into reaction and only a part thereof (which contains the conversion products at the liquid state) flows out of the reactor as liquid component of the biphasic effluent.
  • the presence within the reactor, above the reaction liquid, of biphasic foam that contains significantly more reaction liquid than the biphasic effluent offers the possibility to introduce gas at the biphasic foam in order to counteract the fall of the reaction liquid and force the outflow thereof in the biphasic effluent, without altering the flow regime of the underlying reaction liquid.
  • object of the present invention is a system for hydroconversion of heavy oils in a single reaction stage comprising:
  • a first line for feeding the reactor with heavy oil comprising at least 10% by weight of hydrocarbons having, at atmospheric pressure, a boiling point higher than 540 °C;
  • reaction liquid traversed by said first gas also defined “bubbling liquid”
  • a biphasic foam including at least one liquid phase and one gaseous phase, said biphasic foam originating a biphasic effluent when exiting from the head of the reactor;
  • the hydroconversion system also comprises:
  • a densimeter suitable for measuring the density of said biphasic foam in said upper part of the reactor, in an intermediate position between the gas introduction at said eighth line and said drawing at said fourth line.
  • the densimeter therefore measures the density of the biphasic foam following the intro- duction of said gas in the reactor through the eighth line and the introduction of said second residue through the seventh line.
  • the hydroconversion system comprises a nozzle grid by means of which said second gas can be introduced into the upper part of the reactor.
  • the hydroconversion system comprises a ninth line for drawing, from said seventh line, solids generated during reaction.
  • the hydroconversion system also comprises:
  • Another object of the invention is a method for hydroconversion of heavy oils in a single reaction stage (usable, by way of example, with the system that is the object of the invention) comprising the following steps:
  • heavy oil comprising at least 10% by weight of hydrocarbons having, at atmospheric pressure, a boiling point higher than 540 °C;
  • reaction liquid traversed by said first gas also defined “bubbling liquid”
  • a biphasic foam including at least one liquid phase and one gaseous phase, said biphasic foam originating a biphasic effluent when exiting from the head of the reactor;
  • a second gas is introduced into the upper part of the reactor, at a zone thereof containing said biphasic foam, in addition:
  • step a the second gas being introduced into the upper part of the reactor at a superficial velocity comprised between 0.1 cm/s and 50 cm/s.
  • surface speed of the second gas it is intended the ratio between the flow rate with which, in step a), the second gas is introduced in the reactor, measured at the same temperature and at the same pressure of the latter, expressed in cm 3 per second, and the area of the cross section of the reactor expressed in cm 2 .
  • the superficial velocity of the second gas is therefore expressed in cm per second
  • step b said biphasic effluent being originated with a superficial velocity of the gas equal to at least 10 times the liquid flow velocity.
  • the "superficial velocity of the first gas" i.e. the ratio between the flow rate with which, in step a), the first gas is introduced in the reactor, measured at the same temperature and at the same pressure of the latter, expressed in cm 3 per second, and the area of the cross section of the reac- tor expressed in cm 2
  • liquid flow velocity it is intended the ratio between the flow rate with which, in step b), the liquid phase of the biphasic effluent is drawn from the upper part of the reactor, expressed in cm 3 per second, and the area of the cross section of the reactor expressed in cm 2 .
  • the liquid flow velocity is therefore expressed in cm per second;
  • step a said second gas being introduced into the upper part of the reactor at a temperature such that the temperature of the biphasic foam is comprised between 330 °C and 430 °C;
  • step e) said second residue being introduced in the reactor at a unit flow rate at least equal to 0.5 x Vs x H, where Vs is the space velocity with which, in step a), said heavy oil is introduced in the reactor and H is the height of the reactor.
  • unit flow rate of said second residue it is intended the ratio between the flow rate with which said second residue is introduced in the reactor, expressed in m 3 per hour, and the area of the cross section of the reactor expressed in m 2 .
  • the unit flow rate is therefore expressed in m per hour.
  • space velocity of said heavy oil it is intended the ratio between the flow rate with which said heavy oil is introduced in the reactor, expressed in m 3 per hour, and the volume of the reactor expressed in m 3 . The space velocity is therefore expressed in hours" 1 .
  • the height H of the reactor is expressed in m.
  • step b) said biphasic effluent being originated with a superficial velocity of the gas equal to at least 15 times the liquid flow velocity.
  • step e) said second residue being introduced in the reactor at a unit flow rate at least equal to Vs x H.
  • the superficial velocity of the gas is preferably higher than 2 cm/s, and still more preferably higher than 5 cm/s.
  • step e) solids generated under reaction are drawn from said second residue before the same is introduced in the reactor. The solids generated under reaction are removed by drawing a fraction of said second residue. Also removed with said drawing, in the same proportion with respect to the charge stock, is the possible dispersed catalyst contained therein.
  • the hydroconversion method comprises the following steps:
  • the accumulation factor is not less than 25.
  • step e the solids generated under reaction are drawn from said second residue before the same is introduced in the reactor
  • accumulation factor it is intended the ratio between the flow rate with which, in step a), the heavy oil is introduced in the reactor, expressed in m 3 per hour, and the flow rate with which, in step e), a fraction of said second residue is drawn to purge the solids, expressed in m 3 per hour.
  • the hydroconversion method comprises steps f) to h), by "accumulation factor" it is intended the ratio between the flow rate with which, in step a), the heavy oil is introduced in the reactor, expressed in m 3 per hour, and the flow rate with which, in step f), said fraction of the first residue is drawn in order to be decanted or centrifuged, expressed in m 3 per hour.
  • the accumulation factor is therefore dimensionless.
  • step a) when the reactor is of the type with expanded catalyst bed in which dispersed catalyst is also fed, the expanded catalyst bed only contains silica-alumina support, lacking catal tical- ly-active metals for the purpose of hydrogenation, or it partially or completely lacks said silica-alumina support.
  • step a) when the reactor is of the type with expanded catalyst bed in which dispersed catalyst is also fed, the expanded catalyst bed contains silica-alumina support, lacking catalytically- active metals for the purpose of hydrogenation;
  • step a) when the reactor is of the type with expanded catalyst bed in which dispersed catalyst is also fed, the expanded catalyst bed only contains silica-alumina support, lacking catalytical- ly-active metals for the purpose of hydrogenation;
  • step a) when the reactor is of the type with expanded catalyst bed in which dispersed catalyst is also fed, the expanded catalyst bed lacks silica-alumina support.
  • step a) when the reactor is of the type with dispersed catalyst or it is of the type with expanded catalyst bed in which dispersed catalyst is also fed, the catalyst bed only containing silica- alumina support, or the reactor is of the type with expanded catalyst bed in which only dispersed catalyst is fed (given that the catalyst bed lacks supported catalyst and silica-alumina support), the dispersed catalyst has molybdenum base and the replenishment of said dispersed catalyst is less than 100 ppm of metallic molybdenum with respect to the charge stock being fed.
  • replenishment of the dispersed catalyst it is intended the replenishment made necessary by the removal of dispersed catalyst, which takes place together with the removal of the solids generated under reaction by said first or second residue, in accordance with the abovementioned aspects of the invention.
  • the reactor when the reactor is of the type with expanded catalyst bed (into which dispersed catalyst is also possibly fed), the reactor operates at a degree of conversion not less than 95%.
  • the figure shows a system for hydroconversion of heavy oils, provided with a single reaction stage, comprising a cylindrical reactor 4 of the type with dispersed catalyst or of the type with expanded catalyst bed (in which dispersed catalyst is also possibly fed or in which only dispersed catalyst is fed) provided with a system for introducing gas in a zone containing biphasic foam above the reaction liquid which, as will be illustrated hereinbelow in the present description, produces an entrainment of reaction liquid in the biphasic effluent.
  • the reaction stage can be constituted by several reactors, like the reactor 4, in parallel.
  • the reactor 4 is fed with heavy oil through a line 1 and with hydrogen or gas containing hydrogen, through a line 2.
  • the heavy oil fed through the line 1 comprises at least 10% by weight of hydrocarbons having a boiling point higher than 540 °C so as to have sufficient foaming properties to generate a biphasic foam above the reaction liquid (traversed by hydrogen or by the gas containing hydrogen).
  • the reactor 4 is of the type with expanded catalyst bed (in which also dispersed catalyst is possibly fed or in which only dispersed catalyst is fed), the hydrogen is premixed with the feeding of the heavy oil.
  • the two fluids are distributed at the base of the reactor by means of a perforated plate (not shown in the figure) that supports the catalyst.
  • the hydrogenation catalyst is deposited on a solid support, for example in the form of small cylinders or microspheres.
  • the reactor 4 is fed with the supported catalyst in the upper part thereof through a line not shown in the figure.
  • the reactor 4 is continuously or periodically fed with the supported catalyst to compensate for the spent catalyst that is withdrawn from the lower part of the reactor 4 through a line not shown in the figure.
  • the hydrogen is introduced at the base thereof by means of a nozzle distributor (not shown in the figure).
  • the reactor 4 is fed with the dispersed catalyst at the bottom thereof by means of a line 3, from which the catalyst admixes with the reaction liquid.
  • the reactor 4 is fed with the catalyst to compensate for the quantity of catalyst that is removed with the purge of the solids.
  • the catalyst can be introduced as is or by means of an oil-soluble precursor, i.e. a compound of metal (or metals) soluble in hydrocarbons, capable of generating the active species when it is in contact with the reaction liquid and the hydrogen.
  • Catalysts are preferred with molybdenum base or molybdenum and iron base, possibly comprising silica- alumina or a zeolite compound.
  • the line 3 visible in the figure is therefore only present if the reactor 4 is of the type with dispersed catalyst or is of the type with expanded catalyst bed in which dispersed catalyst is also fed or is of the type with expanded catalyst bed in which only dispersed catalyst is fed.
  • the reactor 4 preferably operates at a temperature comprised between 330 °C and 430 °C, and at a pressure comprised between 10 MPa and 30 MPa. Under reaction conditions, in the upper part of the reactor 4, above the reaction liquid, a biphasic foam is produced which lifts reaction liquid towards the outlet where it generates a biphasic effluent that by means of a line 5 is fed to a gas-liquid separator 6 operating at the same pressure of the reactor 4. At the head of the separator 6, a gaseous flow 7 is obtained from which, via condensation, the light conversion products are recovered along with the excess hydrogen which, after a purification treatment, is recycled to the reactor 4.
  • the reaction liquid which constitutes the liquid phase present in the biphasic effluent, is collected, due to its density, at the bottom of the separator 6 together with the solids produced under reaction (such as coke, insoluble asphaltene resins and sulfides of the metals brought by the heavy oil).
  • the reactor 4 is of the type with dispersed catalyst (or of the type with expanded catalyst bed in which dispersed catalyst is also fed or in which only dispersed catalyst is fed), in the liquid at the separator 6 bottom there is also a quantity of dispersed catalyst with a concentration close to that of reaction.
  • the separator 6 bottom liquid, with the solids produced by the reaction in suspension (and possibly the catalyst if the reactor 4 is fed with dispersed catalyst), is first sent, by means of a line 8, to a stage of flash- atmospheric distillation 9 from which the most volatile conversion products 10 are recovered, and subsequently sent, by means of a line 11 , to a stage of concentration via vacuum distillation 12, with the extraction of the high-boiling conversion products 13 with a final boiling point of 540 °C, possibly lowered in order to obtain the quality specifications (% CCR and % insoluble asphaltenes in n-pentane, first of all) required for the subsequent treatments of hydrocracking and hydrotreating (not shown in the figure).
  • the residue of the vacuum distillation is recycled to the reactor 4 by means of a line 14.
  • a stream is derived that is used for removing the solids generated by the reaction and accumulated in the reaction liquid. This constitutes a first mode of removal from the hydroconversion system of the solids produced by the reaction.
  • a second removal mode will be illustrated hereinbelow in the present description with reference to the lines 18, 20 and 21 , and to the stage 19.
  • the flow rate of reaction liquid which, through the biphasic effluent, reaches the bottom of the separator 6 in order to feed the extraction of the high-boiling conversion products depends on the superficial velocity of the hydrogen introduced at the base of the reactor 4. As stated above, said superficial velocity of the hydrogen cannot however be increased beyond a specific value.
  • a hindered capacity of extraction of reaction liquid via biphasic effluent strongly limits the capacity of hydroconversion of the reactors with dispersed catalyst, as well as of the reactors with expanded catalyst bed of the prior art. In order to increase the aforesaid flow rate of reaction liquid (i.e.
  • the reactor 4 in order to increase the capacity of extraction of the reaction liquid via biphasic effluent), the reactor 4 is provided with a gas entrainment system adapted to facilitate the outflow of reaction liquid from the reactor 4 at the line 5 (i.e. the outlet duct of the reactor 4).
  • a line 16 for introducing gas is positioned, preferably by means of a nozzle grid.
  • the gas preferably but not necessarily comprises hydrogen, and still more preferably hydrogen drawn before the purification treatment and/or recycled hydrogen and/or hydrocarbons at the gas state.
  • a densimeter 17 is installed which detects the density of the biphasic foam.
  • the transfer of reaction liquid into the biphasic effluent exiting at the head of the reactor 4 increases in proportion to the flow rate of gas introduced and in proportion to the density of the biphasic foam measured by the densimeter 17.
  • the flow rate of reaction liquid transferred into the biphasic effluent in relation to the flow rate of gas that enters into the vault can vary from 0.5 kg to 5 kg of liquid per kg of gas, as a function of the density measured by the densimeter 17, in turn connected to the foaming properties of the charge stock.
  • the ratio between the diameter of the reactor 4 and the diameter of the outlet duct of the biphasic effluent is another parameter that determines the degree of the entrainment.
  • the temperature of the gas introduced by means of the line 16 is such that the temperature of the biphasic foam at the head of the reactor 4 is preferably comprised between 330 °C and 430 °C.
  • the flow rate of the residue of the vacuum distillation recycled at the bottom of the reactor 4 (at the line 14) is increased.
  • the correct balance, between said recycled flow rate at the reactor bottom and the flow rate with which the gas at the line 16 is introduced, is verified when the density measured by the densimeter 17 is preferably comprised between 50 kg/m 3 and 500 kg/m 3 , and still more preferably between 100 kg/m 3 and 500 kg/m 3 .
  • the flow rate of reaction liquid which is transferred to the biphasic effluent, and consequently to the bottom of the separator 6, corresponds with the flow rate of residue of the vacuum distillation fed to the reactor 4 bottom summed with the flow rate of the products generated from the conversion of the charge stock, present in liquid form in the reaction liquid.
  • the residue of the vacuum distillation circulated into reaction constitutes the vehicle through which the gases, introduced at the lines 2 and 16, transfer the conversion products to the liquid phase of the biphasic effluent, mainly high- boiling conversion products, present at the liquid state into reaction, to be subsequently recovered outside the reactor 4.
  • the hydroconversion unit capacity of the system thus assumes a value independent of the height of the reactor 4 and adaptable to Vs (of course within the limits allowed by the hydroconversion kinetics depending on the nature of the treated charge stock). From a practical standpoint, the hydroconversion unit capacity is therefore no longer negatively affected by the height of the reactor 4 but is preserved even with the increase of the latter.
  • the superficial velocity of the gas uG (expressed in cm per second) exiting from the reactor 4 (given by the sum of the superficial velocity of the gas introduced at the base of the reactor 4 at the line 2 and the superficial velocity of the entrainment gas introduced in the reactor 4 above the level of the reaction liquid at the line 16) is preferably at least 10 times, and still more preferably at least 15 times, the velocity uL (likewise expressed in cm per second) of the reaction liquid exiting from the reactor 4 (at the line 5).
  • Numerically uL is given by the ratio between the flow rate of reaction liquid exiting from the reactor 4 (which is recovered at the bottom of the separator 6, at the line 8) expressed in cm 3 per second, and the area of the cross section of the reactor 4 expressed in cm 2 .
  • the condition uG > 10 uL, and still more the condition uG > 15 uL, involves an entrainment of liquid into the transport duct 5 of the biphasic effluent not less than the liquid coming from the reactor, which maintains the liquid-foam interface within the reactor itself.
  • flow rates of gas are introduced such to involve values of uG preferably greater than 2 cm/s, and still more preferably greater than 5 cm/s.
  • flow rates of gas are introduced such to involve values of uG comprised between 7 and 12 cm/s in order to extract the liquid conversion products generated by a reactor of height equal to 30 meters, fed with charge stock at a space velocity of 0.25 h "1 .
  • the superficial velocity of the gas at the line 16 is preferably comprised between 0.1 cm/s and 50 cm/s. If the reactor 4 is of the type with expanded catalyst bed (in which also dispersed catalyst is possibly fed or in which only dispersed catalyst is fed), the possibility of increasing the quantity of high-boiling conversion products present in the biphasic effluent, operating on the flow rate of entrainment gas introduced at the line 16 and on the flow rate of the residue of the vacuum distillation recycled at the bottom of the reactor 4, allows operating the reactor 4 in a single reaction stage, avoiding the placement of several reactors in series one to the other in order to facilitate the extraction of the conversion products.
  • a second flow of reaction liquid (not shown in the figure) can be extracted from a zone of the reactor containing bubbling liquid free of solids.
  • the drawn liquid is sent to a degasser in order to obtain the reaction liquid from which the volatile conversion products are extracted via flash and distillation, and subsequently the high-boiling conversion products are extracted via vacuum distillation.
  • the introduction of the gas at the head of the reactor 4 at the line 16 is carried out by respecting the above- indicated density limits of the biphasic foam (preferably between 50 kg/m 3 and 500 kg/m 3 , and still more preferably between 100 kg/m 3 and 500 kg/m 3 ) and ensuring a ratio between the superficial velocity of the gas uG and the velocity of the liquid uL exiting at the head of the reactor 4 preferably of at least 10, and still more preferably of at least 15.
  • the vacuum distillation extracts the conversion products contained both in the liquid phase present in the biphasic effluent from the head of the reactor 4, and in the liquid obtained directly from the bubbling zone.
  • the unit flow rate of the residue of the vacuum distillation recycled at the bottom of the reactor 4 is, also in such case, tied to the height H of the reactor 4 and to the space velocity Vs with which the charge stock is fed.
  • the unit flow rate of the residue of the vacuum distillation recycled at the bottom of the reactor 4 is preferably greater than 0.5 x Vs x H, and still more preferably greater than Vs x H.
  • the products of hydroconversion of the charge stock are obtained.
  • the solids generated by the reaction are accumulated in the reaction liquid as solid phase in suspension (present in the different sections that constitute the hydroconversion system).
  • said solids are removed by drawing, from the line 14, a fraction of the liquid suspension, residue of the vacuum distillation (where the solids are concentrated), and purging such fraction at the line 15.
  • the liquid phase present in such stream 15 corresponds to the non-converted charge stock which, exiting as is from the hydroconversion system, determines the difference with respect to the 100% of the attainable conversion degree. In order to minimize the purge of non-converted charge stock and hence increase the conversion degree, it is necessary to reduce the formation of solids under reaction.
  • the sulfides of the metals brought by the charge stock 1 are present, together with possibly the catalyst fed in dispersed form and the "fines" generated by the supported catalyst.
  • solids of organic nature are usually present, but in much greater quantity; these are constituted by insoluble asphaltene resins and by coke, no longer convertible, to be removed.
  • the production of insoluble resins and coke can be reduced until it is eliminated by lowering the reaction temperature in order to facilitate the hydrogenation reactions and at the same time prevent the undesired reactions that via dehydrogenation lead to the formation of insoluble resins and coke.
  • the system of extraction of the conversion products at the liquid state via entrainment gas and vacuum recycling since it assures a suitable extraction of the conversion products, even operating at low reaction temperature, is an enabling factor for operating the hydroconversion of a specific charge stock in the most favorable low reaction temperature conditions, without having to otherwise suffer unsustainable capacity reduction.
  • the reaction temperature can be limited in a manner such to involve a formation of total solids, inorganic and organic, that is limited within 0.003 kg per kg of fed charge stock.
  • One such production level of solids allows operating the purge at the line 15 at flow rates less than 5% of the charge stock feed flow rate, determining a conversion degree at least equal to 95%, regardless of whether reactors employed are of the type with dispersed catalyst or of the type with expanded catalyst bed.
  • a second mode with which the removal of the solids produced by the reaction occurs by deriving the liquid suspension that contains such solids before the concentration step.
  • a flow 18 is derived that is subjected to centrifugation or settling by decanter at a stage indicated with the reference number 19.
  • the centrifuge or decanter allows separating the solids (collected at a line 20 in order to be purged) from the liquid phase (drawn at a line 21 ) which is rejoined to the flow at the line 11 in order to feed the vacuum extraction of the high-boiling conversion products.
  • the liquid purge stream at the line 15 can be omitted, thus eliminating the purge of non- converted charge stock.
  • the solids produced by the reaction along with the dispersed catalyst fed to the reactor 4 (if the latter is of the type with dispersed catalyst or is of the type with expanded catalyst bed in which dispersed catalyst is also fed or in which only dispersed catalyst is fed), are accumulated in the hydroconversion system.
  • the purge of the solids is carried out "in suspension phase” it is intended that the solids are suspended in the liquid flow at the line 15. From the latter, part of the liquid flows out that comes from the bottom of the vacuum distillation, which contains the solids in suspension (i.e. in suspended or dispersed form).
  • the purge of the solids is operated in suspension at the line 15, or whether the solids are removed in solid form at the line 20, it is possible to define an "accumulation factor".
  • the accumulation factor is given by the ratio between the flow rate of charge stock being fed at the line 1 and the flow rate of the stream at the line 15.
  • the accumulation factor is given by the ratio between the flow rate of charge stock being fed at the line 1 and the flow rate of the liquid suspension at the line 18.
  • the flow rate of the stream 15 or the flow rate of the stream 18 (depending on the mode used for removing the solids) is minimized for the purpose of maximizing the aforesaid accumulation factor.
  • High values of the accumulation factor even if not involving significant advantages in terms of attainable conversion degree (given that this is in any case higher than 95%, and close to 100% when one proceeds with the removal of the solids in solid form at the line 20), nevertheless offer the great advantage of minimizing the replenishment of catalyst in the reactors with dispersed catalyst, in the reactors with expanded catalyst bed in which dispersed catalyst is also fed and in the reactors with expanded catalyst bed in which only dispersed catalyst is fed.
  • the system of accumulation-removal of solids described herein, in suspension, via stream 15 or in solid form, at the line 20, involves concentrations of catalyst in the reaction liquid that are increased with respect to the metered catalyst amounts, referred to the charge stock being fed.
  • concentrations of catalyst in the reaction liquid that are increased with respect to the metered catalyst amounts, referred to the charge stock being fed.
  • an accumulation factor at the line 18 equal, by way of example, to 25
  • a metering of catalyst, e.g. molybdenum, of 50 ppm, referred to the charge stock being fed involves a concentration of catalyst in the line 18 of 1250 ppm corresponding with a concentration of catalyst in the reaction liquid within the reactor 4 (which in terms of solids is less concentrated than the flow at the line 18) of around 1000 ppm.
  • catalyst concentrations are obtained into reaction equal to at least 20 times the metering of dispersed catalyst referred to the charge stock being fed.
  • a specific value of the accumulation factor, detected at the line 18, is associated with a numerically larger value of the accumulation factor detected at the line 15.
  • the accumulation factor will always be that detected at the line 18.
  • the reactor 4 is of the type with dispersed catalyst or of the type with expanded catalyst bed in which dispersed catalyst is also fed or is of the type with expanded catalyst bed in which only dispersed catalyst is fed, by following the system of accumulation and removal of solids described above, even if operating at low catalyst replenishment (i.e. with low catalyst consumption), the concentration of the dispersed catalyst in the reaction liquid reaches levels such to ensure the attainment of the maximum catalytic effect, hence rendering uselessly expensive the simultaneous presence of metals in supported form catalytically-active for the hydrogenation (such as molybdenum, chromium, vanadium) when reactors employed are of the type with expanded catalyst bed in which dispersed catalyst is also fed.
  • concentration of the dispersed catalyst in the reaction liquid reaches levels such to ensure the attainment of the maximum catalytic effect, hence rendering uselessly expensive the simultaneous presence of metals in supported form catalytically-active for the hydrogenation (such as molybdenum, chromium, vanadium) when reactors employed are of the type
  • the expanded catalyst bed is occupied by the structured support (small cylinders or microspheres), constituted only by silica-alumina or another acid reaction material (like the zeolites), in order to support the denitrification of the charge stock.
  • the structured solid acid reaction material confined inside the reactor, no longer performing the function of support of the catalytically-active metals for the purpose of hydrogenation, can be present in significantly reduced quantity or be totally eliminated, with consequent recovery of useful reaction volume and reduction of the formation of "fines" to be removed.
  • the reactor of the type with expanded catalyst bed is only fed with dispersed catalyst.
  • the acid reaction component (silica, alumina or zeolite compound), if of interest, can be fed in dispersed form. In such case, the recirculation of the reaction liquid by means of the "ebullating pump" can be limited or omitted.
  • reactor with expanded catalyst bed it is intended a reactor with expanded catalyst bed in which dispersed catalyst is also fed or a reactor with expanded catalyst bed in which only dispersed catalyst is fed (i.e. in which the silica-alumina structured solid material is absent).

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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

La présente invention concerne un système d'hydroconversion d'huiles lourdes dans un étage réactionnel unique, qui utilise des réacteurs à catalyseur dispersé ou lit de catalyseur expansé, dans lesquels l'extraction du liquide réactionnel à travers l'effluent biphasique est améliorée par l'introduction de gaz au niveau de la tête du réacteur, dans une zone contenant de la mousse biphasique au-dessus du liquide réactionnel. L'introduction de gaz au niveau de la tête du réacteur améliore l'extraction à l'état liquide des produits de conversion à point d'ébullition élevé. Le but est : d'améliorer la capacité de l'unité d'hydroconversion d'un réacteur, en la rendant simultanément indépendante de la hauteur du réacteur ; dans le cas de réacteurs à lit de catalyseur expansé, le fonctionnement de tels réacteurs dans un étage réactionnel unique à degré élevé de conversion ; et dans le cas de réacteurs à catalyseur dispersé ou à lit de catalyseur expansé dans lequel le catalyseur dispersé est également alimenté ou à lit de catalyseur expansé dans lequel uniquement le catalyseur dispersé est alimenté et est présent, réduisant la consommation de ce dernier. L'invention désigne également un procédé d'hydroconversion d'huiles lourdes qui peut être actionné à l'aide du système constituant l'objet de l'invention.
PCT/IT2015/000247 2015-08-06 2015-10-02 Système et procédé d'hydroconversion d'huiles lourdes à l'aide de réacteurs à catalyseur dispersé ou avec un lit de catalyseur expansé avec introduction de gaz au niveau de la tête du réacteur WO2017021987A1 (fr)

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ITUB2015A002927A ITUB20152927A1 (it) 2015-08-06 2015-08-06 Sistema e metodo di idroconversione di oli pesanti mediante reattori a catalizzatore disperso o a letto catalitico espanso con immissione di gas alla testa del reattore
IT102015000042650 2015-08-06

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IT201800005448A1 (it) * 2018-05-16 2019-11-16 Idroconversione di oli pesanti a migliorate velocità di idrogenazione e capacità di evaporazione
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IT201900022842A1 (it) * 2019-12-03 2021-06-03 Luigi Patron Processo per l’idroconversione di oli idrocarburici pesanti a ridotto consumo di idrogeno a conversione completa

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CN111482138A (zh) * 2019-01-29 2020-08-04 南京延长反应技术研究院有限公司 低压气液强化乳化床反应装置及方法
CN111482137A (zh) * 2019-01-29 2020-08-04 南京大学 上置式渣油加氢乳化床微界面强化反应装置及方法
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