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
• • 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
  • C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
• • 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
  • C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
  • C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel 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
  • 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
  • C10G2300/201—Impurities
  • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
• • 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
  • C10G2400/02—Gasoline
• • 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
• • 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
• • 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
  • C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
  • C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
  • C10G70/06—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by gas-liquid contact

Definitions

• the present invention relates to the field of hydrocarbon feed hydrotreatment processes, preferably of diesel type.
• the objective of the process is the production of a hydrocarbon stream, preferably of diesel, desulfurized.
• the purpose of the hydrotreatment process is to transform a hydrocarbon feedstock, in particular a gas oil fraction, in order to improve its characteristics with regard to the presence of sulfur or other heteroatoms such as nitrogen but also by decreasing the content of aromatic hydrocarbon compounds by hydrogenation and thus improving the cetane number.
• the hydrotreating process of hydrocarbon cuts is intended to eliminate the sulfur or nitrogen compounds contained therein in order, for example, to bring a petroleum product to the required specifications (sulfur content, aromatic content, etc.). for a given application (automotive fuel, gasoline or diesel, heating oil, jet fuel).
• the tightening of automobile pollution standards in the European Community has forced refiners to drastically reduce the sulfur content in diesel fuels and gasoline (up to 10 parts per million weight (ppm) of sulfur as of 1 January 2009, compared to 50 ppm as of January 1, 2005).
• the desulphurized gas oil is produced by a conventional method comprising heating the diesel fuel charge with hydrogen in an oven, and then the feed is introduced into a hydrodesulfurization unit containing a catalyst so hydrodesulphurize the charge.
• the document US Pat. No. 5,409,599 describes an improved hydrodesulphurization process, similar to the diagram represented by FIG. 6.
• the charge 201 is fractionated in the column C2 into a light fraction 202 and a heavy fraction 203.
• the heavy fraction 203 is introduced into a first reactor R1, then the effluent of the first reactor R1 and the light fraction 202 are mixed and introduced into a second reactor R2.
• the present invention proposes to optimize the process described by the document
• the present invention proposes to extract H 2 S and NH 3 contained in the effluent from the first reactor and to maximize the flow rate of pure hydrogen introduced into the reactor. the second reactor to improve the hydrodesulphurization performance in the second reactor.
• the invention describes a process for the hydrotreatment of a hydrocarbon feedstock comprising sulfur and nitrogen compounds, in which the following steps are carried out:
• a) the hydrocarbon feedstock is separated into a fraction enriched in heavy hydrocarbon compounds and a fraction enriched in light hydrocarbon compounds
• a first hydrotreatment step is carried out by contacting the fraction enriched with heavy hydrocarbon compounds and a gaseous flow comprising hydrogen with a first hydrotreatment catalyst in a first reaction zone to produce a first desulfurized effluent comprising hydrogen, H 2 S and NH 3 ,
• the first gaseous fraction is purified to produce a hydrogen-enriched stream
• the enriched fraction of light hydrocarbon compounds is mixed with the first liquid fraction obtained in step c) to produce a mixture
• a second step of hydrotreating by contacting the mixture obtained in step e) and at least a portion of the hydrogen-enriched stream produced in step d) with a second hydrotreatment catalyst in a second reaction zone Z2 to produce a second desulfurized effluent comprising hydrogen, NH 3 and H 2 S,
• steps b) f) g) and h) can be carried out in a reactor, the first reaction zone and the second reaction zone being disposed in said reactor, the reaction zone being separated from the reaction zone. reaction by a liquid-tight and gas-permeable tray, the second liquid fraction being collected by said tray, the second gaseous fraction flowing from the first zone to the second zone through said tray.
• Hydrogen can be supplemented so as to perform the second hydrotreating step in the presence of said hydrogen booster, said hydrogen booster comprising at least 95% by volume of hydrogen.
• the first reaction zone can be implemented under the following conditions:
• Step d) may carry out an amine wash step to produce said hydrogen enriched stream.
• the first effluent can be separated into a first liquid stream and a first gas stream, said first gas stream can be partially condensed by cooling and the first partially condensed stream can be separated into a second liquid stream and a second one.
• second gaseous stream and in step d) the first and second gaseous streams can be brought into contact with an absorbent solution comprising amines to produce said hydrogen-enriched stream.
• said hydrogen-enriched stream Prior to performing step e), said hydrogen-enriched stream can be contacted with a capture mass to reduce the water content of said hydrogen-enriched stream.
• Step a) can be carried out in a distillation column.
• the first catalyst and the second catalyst may be independently selected from catalysts composed of a porous mineral carrier, at least one metal element selected from group VI B and a metal element selected from group VIII.
• the first and second catalysts may be independently selected from a catalyst composed of cobalt and molybdenum deposited on a porous support based on alumina and a catalyst composed of nickel and molybdenum deposited on a porous carrier based on alumina.
• the hydrocarbon feed may be composed of a slice whose initial boiling point is between 100 ° C and 250 ° C and the final boiling point is between 300 ° C and 450 ° C.
• FIG. 1 schematizes the principle of the method according to the invention
• FIGS. 2, 3 and 4 show three embodiments of the method according to the invention
• FIG. 5 represents a conventional hydrodesulfurization process
• FIG. 6 represents a hydrodesulfurization scheme similar to the process described in the document US Pat. No. 5,409,599.
• the hydrocarbon feedstock to be treated arrives via line 1.
• the hydrocarbon feed may be a kerosene and / or a diesel fuel.
• the hydrocarbon feed may be a cut whose initial boiling point is between 100 ° C. and 250 ° C., preferably between 100 ° C. and 200 ° C.
• the final boiling point is between 300 ° C. and 450 ° C. C, preferably between 50 ° C and 450 ° C.
• the hydrocarbon feedstock may be chosen from an atmospheric distillation cut, a cut produced by vacuum distillation, a cut resulting from catalytic cracking (commonly known as "LCO cut” for Light Cycle Oil according to the Anglo-Saxon terminology) or a cut resulting from a heavy charge conversion process, for example a coking, visbreaking, and residue hydro-conversion process.
• the feedstock comprises sulfur compounds, generally at a content of at least 1000 ppm by weight of sulfur, or even more than 5000 ppm by weight of sulfur.
• the feedstock also comprises nitrogen compounds, for example the feedstock comprises at least 50 ppm by weight of nitrogen, or at least 100 ppm by weight of nitrogen.
• the feedstock is split into two sections in the SEP unit to produce a light fraction discharged through line 2 and a heavy fraction discharged through line 3.
• the SEP unit may use a distillation column, a fractionation balloon between a gaseous phase and a liquid phase, a stripping column.
• the heavy fraction has a higher boiling point than the light fraction.
• the heavy fraction arriving via line 3 is mixed with a stream comprising hydrogen arriving via line 8.
• the heavy fraction may optionally be heated before it is introduced into reaction zone Z1. Then the mixture is introduced into the reactor zone Z1.
• the reaction zone Z1 comprises at least one hydrotreatment catalyst. If necessary, before introduction into Z1, the mixture can be heated and / or relaxed.
• the mixture of the heavy fraction and hydrogen is introduced into the reaction zone Z1 to be brought into contact with a hydrotreatment catalyst.
• the hydrotreatment reaction makes it possible to decompose the impurities, in particular the impurities containing sulfur or nitrogen, and possibly to partially remove the aromatic hydrocarbon compounds and more particularly the polyaromatic hydrocarbon compounds.
• the destruction of impurities leads to the production of a hydrorefined hydrocarbon product and an acid gas rich in H 2 S and NH 3 , gases known to be inhibitors and even in some cases poisons hydrotreatment catalysts.
• This hydrotreatment reaction also makes it possible to partially or completely hydrogenate the olefins, and partially the aromatic nuclei. This makes it possible to reach a content of low polyaromatic hydrocarbon compounds, for example a content of less than 8% by weight in the treated gas oil.
• the reaction zone Z1 can operate with the following operating conditions:
• the liquid velocity in the reaction zone Z1 may be at least 2 mm / s
• the operating conditions of the reaction zone Z1 and the catalyst contained in zone Z1 can be chosen to reduce the sulfur content so that the sulfur content in the effluent from zone Z1 is lowered to a content of between between 50 and 500 ppm by weight.
• the hydrogenation reactions of sulfur compounds that are easiest to perform are carried out in zone Z1.
• the effluent from the reaction zone Z1 via the conduit 4 is introduced into the separation device D1 in order to separate a liquid fraction containing the hydrocarbons from the heavy fraction and a gaseous fraction rich in hydrogen, H 2 S and NH 3 .
• the separating device D1 can implement one or more separation tanks between gas and liquid, possibly with heat exchangers for partially condensing the gas flows.
• the liquid fraction is removed from D1 via line 6.
• the gaseous fraction is removed from D1 via line 5.
• at least a portion of the effluent from the zone Z1 can be brought into contact with the water injected via line 26 into the device D1. In this case, an aqueous liquid fraction containing NH 3 of the device D1 is discharged via the conduit 6b.
• D1 contains the sulfur compounds of the heavy fraction most refractory to hydrogenation reactions.
• the hydrocarbon liquid fraction is sent via line 6 to zone Z2 in order to hydrogenate the sulfur compounds that are the most refractory to the hydrogenation reactions.
• the gaseous fraction rich in H 2 S and NH 3 circulating in line 5 is introduced into an LA amine washing unit.
• the gas fraction rich in H 2 S and NH 3 and containing hydrogen is contacted with an absorbent solution containing amines.
• the acid gases are absorbed by the amines, which makes it possible to produce a stream enriched in hydrogen.
• FR2907024 and FR2897066 disclose amine scrubbing processes which can be implemented in the LA amine washing unit.
• the stream enriched with hydrogen may optionally be brought into contact with adsorbents to remove the water in particular.
• the gas enriched in hydrogen may comprise at least 95% by volume, or even more than 99% by volume, or even more than 99.5% by volume of hydrogen.
• the hydrogen-enriched gas is discharged from the unit LA via the pipe 10, possibly compressed by a compressor and recycled to the reaction zone Z2 by being mixed with the light fraction arriving via the pipe 2.
• the hydrogen mixture and the light fraction arriving via line 2 can be made in the reaction zone Z2.
• the hydrogen-enriched gas discharged from unit LA via line 10a is recycled to the separation unit SEP in order to promote stripping separation: the flow of hydrogen entrains the light compounds of charge 1.
• a large portion, more than 70% or even more than 95% by volume, of the hydrogen arriving via line 10a is found in the light fraction circulating in line 2.
• a refill in fresh hydrogen can be provided by the conduit 1 1.
• the conduit 1 1 makes it possible to introduce hydrogen into the light fraction circulating in the duct 2.
• the flow of hydrogen arriving via the duct 11 can be produced by a process commonly known as "steam reforming of natural gas” or “ steam methane reforming "to produce a flow of hydrogen from water vapor and natural gas.
• the flow of hydrogen 11 may contain at least 95%, or even more than 98% by volume, or even more than 99% by volume of hydrogen.
• the hydrogen stream can be compressed to be at the operating pressure of the reaction zone Z2.
• the flow of hydrogen 1 1 comes from a source external to the process, that is to say that it is not composed of a part of an effluent produced by the process.
• the fresh hydrogen filling can be provided by the conduit
• the hydrogen flow causes the light compounds of the charge 1.
• a large portion, more than 70% or even more than 95% by volume, of the hydrogen arriving via line 11a is found in the light fraction circulating in line 2.
• the light fraction comprising hydrogen arriving via line 2 is optionally heated and then mixed with the hydrocarbon liquid fraction arriving via line 6.
• the pressure of the hydrocarbon liquid fraction discharged from Z1 via line 6 can be raised by means of the P1 pump to be at the operating pressure of the reaction zone Z2. Then the mixture is introduced into the zone of Z2 reaction.
• the reaction zone Z2 comprises at least one hydrotreatment catalyst. If necessary, before introduction into the reaction zone Z2, the mixture can be heated and / or expanded.
• the mixture of the light fraction and the hydrocarbon liquid fraction is introduced into the reaction zone Z2 to be contacted with a hydrotreatment catalyst.
• the hydrotreatment reaction makes it possible to decompose the impurities, in particular the impurities containing sulfur or nitrogen, and possibly to partially remove the aromatic hydrocarbon compounds and more particularly the polyaromatic hydrocarbon compounds.
• the destruction of the impurities leads in particular to the production of a hydrorefined hydrocarbon product and an acid gas rich in H 2 S and NH 3 .
• the fact of sending purified hydrogen, that is to say without or without inhibiting compounds, in particular H 2 S and NH 3 , of the hydrogenation reaction in zone Z2 makes it possible to maximize the partial pressure of hydrogen in zone Z2 in order to carry out the most difficult hydrogenation reactions there.
• the flow of purified hydrogen comes from the LA amine washing unit and optionally the hydrogen filling arriving via the conduit 1 1.
• the entire stream from the LA amine washing unit is introduced into zone Z2.
• the hydrogen present in zone Z2 comes solely and directly from the hydrogen-rich stream coming from the unit LA and from the hydrogen booster arriving via line 11.
• the reaction zone Z2 can operate with the following operating conditions:
• the pressure of Z2 is greater than the pressure of Z1, for example the pressure of Z2 is 0.5 bar, or even 1 bar less than the pressure of Z1, preferably the pressure of Z2 is greater than a value of between 0.5 bar and 5 bar, preferably between 1 bar and 3 bar with respect to the pressure of Z1,
• the effluent from the reaction zone Z2 via the conduit 7 is introduced into the separation device D2 in order to separate a liquid fraction containing the hydrocarbons and a gaseous fraction rich in hydrogen, H 2 S and NH 3 .
• the separation device D2 can implement one or more separation flasks, possibly with heat exchangers for condensing the gas flows.
• the liquid fraction is removed from D2 through line 9.
• This liquid fraction is the product of the process according to the invention, for example the gas oil depleted of sulfur, nitrogen and aromatic compounds.
• the gaseous fraction is removed from D2 via line 8.
• the gaseous fraction is recycled via line 8 to be mixed with the heavy fraction circulating in line 3.
• the separation device D2 performs a single separation step between gas and liquid of the effluent arriving via line 7.
• D2 implements only a separation device between gases and liquid.
• the gaseous fraction resulting from the separation in D2 is sent directly to zone Z1, preferably without undergoing purification treatment and without cooling.
• the gaseous fraction from D2 contains hydrogen but also H 2 S and NH 3 .
• the fact of sending these compounds H 2 S and NH 3 in zone Z1 does not impair the process according to the invention because the simplest hydrogenation reactions take place in zone Z1.
• the entire gaseous fraction from the separation device D2 is directly introduced into the zone Z1.
• the method according to the invention has the advantage of being able to integrate the reaction zones Z1 and Z2, as well as the separation device D2, in the same reactor as described with reference to FIGS. 2, 3 and 4.
• the process according to the invention makes it possible to adapt the separation step in the SEP unit, for example the cutting point in the case of a distillation, during the cycle and thus to reduce the liquid fraction treated in the unit. the reaction zone Z1 while using the same hydrogen flow rates which will have a beneficial effect on the hydrogenation reactions.
• This flexibility makes it possible to adapt the flow rate treated between the reaction zone Z1 and the reaction zone Z2 as a function of the aging of the catalyst and, therefore, of the decrease in performance of the catalyst.
• the operating temperature of the reaction zone Z1 can be selected independently of the operating temperature of the reaction zone Z2.
• the pressure in the reaction zone Z2 may be greater than that of the reaction zone Z1, which is favorable to the hydrotreatment reactions and therefore positive since it is in this zone Z2 that the most active compounds are treated. refractory to hydrotreatment reactions.
• the reaction zones Z1 and Z2 may contain catalysts of identical compositions or catalysts of different compositions.
• one or more catalyst beds of identical composition can be arranged, or several catalyst beds, the composition of the catalysts being different from one bed to another.
• a catalytic bed may optionally be composed of different catalyst layers.
• the catalysts employed in reaction zones Z1 and Z2 may generally comprise a porous mineral support, at least one metal or metal compound of group VIII of the periodic table of elements (this group especially comprising cobalt, nickel, iron, etc.) and at least one metal or metal compound of group VIB of said periodic classification (this group including in particular molybdenum, tungsten, etc.).
• the sum of metals or metal compounds, expressed as weight of metal relative to the total weight of the finished catalyst is often between 0.5 and 50% by weight.
• the sum of metals or compounds of metals of group VI II, expressed in weight of metal relative to the weight of the finished catalyst is often between 0.5 and 15% by weight, preferably between 1 and 10% by weight.
• the sum of the metals or compounds of Group VIB metals, expressed in weight of metal relative to the weight of the finished catalyst is often between 2 and 50% by weight, preferably between 5 and 40% by weight.
• the porous inorganic support may comprise, without limitation, one of the following compounds: alumina, silica, zirconia, titanium oxide, magnesia, or two compounds chosen from the preceding compounds, for example silica-alumina or alumina-zirconia, or alumina-titanium oxide, or alumina-magnesia, or three or more compounds selected from the foregoing compounds, for example silica-alumina-zirconia or silica-alumina-magnesia.
• the support may also comprise, in part or in whole, a zeolite.
• the catalyst preferably comprises a support composed of alumina, or a support composed mainly of alumina (for example from 80 to 99.99% by weight of alumina).
• the porous support may also comprise one or more other promoter elements or compounds, based for example on phosphorus, magnesium, boron, silicon, or comprising a halogen.
• the support may, for example, comprise from 0.01 to 20% by weight of B 2 0 3 , or of SiO 2 , or of P 2 O 5 , or of a halogen (for example chlorine or fluorine), or 0, 01 to 20% by weight of an association of several of these promoters.
• Common catalysts are, for example, catalysts based on cobalt and molybdenum, or on nickel and molybdenum, or on nickel and tungsten, on an alumina support, this support may comprise one or more promoters as previously mentioned.
• the catalyst may be in oxide form, that is to say that it has undergone a calcination step after impregnation of the metals on the support.
• the catalyst may be in an additivated dried form, that is to say that the catalyst has not undergone a calcination step after impregnation of the metals and an organic compound on the support.
• FIGS. 2, 3 and 4 describe three embodiments of the method generally described with reference to FIG. 1, in which the reaction zones Z1 and Z2, as well as the separation device D2, are grouped together in the same reactor R1.
• the reactor R1 may be of cylindrical shape whose axis is vertical.
• the reaction zone Z1 is located below the zone Z2 in the reactor R1.
• the separating device D2 of FIG. 1 takes the form of the plate P in FIGS. 2, 3 and 4.
• a separating plate P is arranged between the zone Z2 and the zone Z1.
• the plate P allows to circulate the gas from the zone Z2 in the zone Z1.
• the plate P is liquid-tight.
• the liquid circulating in the zone Z2 is collected by the plate P to be discharged from the reactor R1 through line 9.
• the feedstock arriving via line 1 is fractionated in two sections in distillation column C.
• effluent is discharged through line 20.
• the bottom of column C is provided with a reboiler R which makes it possible to vaporize a portion of the effluent discharged at the bottom of the column C through the conduit 20 and to reintroduce this portion in vapor form at the bottom of the column C via the conduit 21.
• the other part of the effluent 20 is discharged through line 3.
• the effluent discharged at the top of column C is cooled in heat exchanger E1 to be condensed. Part of the condensate 22 is recycled to the top of column C as reflux.
• the other part of the effluent condensed by the exchanger E1 is discharged through line 2.
• distillation column C makes it possible to produce a light fraction discharged through line 2 and a heavy fraction discharged through line 3.
• Distillation column C can be operated to make a cut at a cutting point of between 260.degree. 350 ° C, that is to say that the light fractionreporte compounds vaporizing at a temperature below the temperature of the cutting point and the heavy fraction comprises compounds vaporizing at a temperature above the temperature of the cutting point.
• the heavy fraction arriving via the pipe 3 is introduced into the lower part of the reactor R comprising the reaction zone Z1 after being optionally heated in an exchanger or in an oven.
• the heavy fraction is introduced into the reactor R between the plate P and the zone Z1.
• the heavy fraction is mixed with a stream of hydrogen, H 2 S and NH 3 arriving from the zone Z2 via the separating plate P. Then the mixture passes through the reaction zone Z1.
• the effluent from zone Z1 is discharged from the reactor via line 4 to be introduced into separator tank B1.
• the flask B1 makes it possible to separate a first hydrocarbon liquid fraction discharged via the duct 23 and a first gaseous fraction discharged through the duct 24.
• the first gaseous fraction flowing in the duct 24 is cooled by the heat exchanger E2 so as to be partially condensed.
• the exchanger E2 condenses the majority of the hydrocarbons contained in the effluent 24 and retains the majority of hydrogen, NH 3 and H 2 S in gaseous form.
• the partially condensed stream from E2 is introduced into separator tank B2 in order to separate a second liquid fraction containing hydrocarbons and a second gaseous fraction rich in hydrogen, NH 3 and H 2 S.
• the hydrocarbon liquid fraction is removed from B2.
• the gas fraction is discharged from B2 via line 5.
• the hydrocarbon-rich liquid fractions discharged through lines 23 and 25 are combined, pumped by pump P1 to be sent via line 6 to zone Z2.
• a stream of water may be added through line 26 to the gas fraction circulating in line 24 to allow the NH 3 present in the gaseous fraction to dissolve in an aqueous fraction.
• the aqueous fraction containing the dissolved NH 3 is also separated in the flask B2, the aqueous fraction being evacuated via the duct 6b.
• part or all of the hydrocarbon liquid fraction from B2 via line 25 is removed from the process via line 25b as a desulfurized cut, for example as a desulphurized gas oil cut.
• this hydrocarbon liquid fraction may be specifications in terms of sulfur, nitrogen and content of aromatic hydrocarbon compounds.
• the flow of hydrogen and acid gas flowing in the conduit 5 is introduced into the LA amine washing unit.
• the hydrogen-rich stream discharged from LA through line 10 is compressed by compressor K1 to be introduced into reactor R at the top of reaction zone Z2.
• a booster of hydrogen may be added to the process via line 11 to improve the reaction in zone Z2.
• the hydrogen filling is introduced via the pipe 1 1 to the flows of hydrogen circulating in the duct 10.
• the light fraction arriving via line 2 is mixed with the hydrocarbon stream arriving via line 6 after having been optionally heated in a heat exchanger and / or in an oven.
• the mixture is introduced into the reactor R at the top of the reaction zone Z2.
• the hydrocarbons arriving via line 6 mix with the hydrogen arriving via line 10.
• the mixture of hydrocarbons and hydrogen passes through reaction zone Z2.
• the gas and the liquid composing the effluent leaving the reaction zone Z2 are separated by the plate P: the gas flows through the plate P to arrive in the reaction zone Z1, the liquid collected by the plate P is evacuated the reactor R through the conduit 9.
• it can implement a separator plate provided with orifices which are extended upwards by tube portions. The upper part of the tube portions are covered by hats.
• the descending liquid is collected by the tray, the tubular portion preventing the liquid from passing through the holes.
• a conduit passing through the wall of the reactor R1 makes it possible to evacuate the liquid collected on the plate.
• the descending gas passes through the tubes and orifices of zone Z2 to zone Z1.
• FIG. 3 proposes a variant of the method according to the invention with respect to the embodiment of FIG. 2.
• the modification relates to the step of fractionation of the feedstock into a heavy fraction and a light fraction.
• the references of FIG. 3 identical to the references of FIG. 2 denote identical elements.
• charge is introduced via line 1 at the top of distillation column C and the makeup flow of hydrogen is introduced via line 11 at the bottom of column C.
• To modify the conditions of the column C it is possible in particular to modify the flow rate and / or the temperature of the reboil flow produced by the reboiler R, and / or the temperature of the feedstock introduced via the duct can be modified. 1 in column C.
• the distillation column C makes it possible to produce a light fraction discharged through line 2 and a heavy fraction discharged through line 3. In this embodiment, a large portion, more than 70%, or even more than 95 % volumic, hydrogen arriving via the conduit 1 1 is found in the light fraction flowing in the conduit 2.
• FIG. 4 proposes a variant of the method according to the invention with respect to the embodiment of FIG. 2.
• the modification relates to the step of fractionation of the feedstock into a heavy fraction and a light fraction.
• the references of FIG. 4 identical to the references of FIG. 2 denote identical elements.
• charge is introduced via line 1 at the top of separation column C and at least part of the hydrogen flow produced by the LA amine washing unit is introduced through lines 10 and 10a at the bottom of column C.
• the remaining fraction of the hydrogen arriving via line 10 is introduced via line 10b to the outgoing flow at the top of the column flowing in line 2.
• the column C may be devoid of reboiler.
• the process of FIG. 5 corresponds to the conventional process in which all the diesel fuel is treated in a single reactor.
• the charge arriving via line 101 is mixed with hydrogen arriving via line 102.
• the mixture is heated in heat exchanger E101, and then it is introduced into reactor R101 for be contacted with a hydrotreatment catalyst.
• the effluent from the reactor R101 is cooled by the heat exchanger E102 to be partially condensed, before being introduced into the separator tank B101.
• the liquid hydrocarbons are discharged at the bottom of the flask B101 via the duct 103.
• the acid gas containing hydrogen, H 2 S and NH 3 is discharged at the top of the flask E101 via the duct 104 to be introduced into the flask.
• LA1 amine wash unit The hydrogen-rich stream obtained from unit LA1 is compressed and then recycled via line 102 to exchanger E101.
• the conduit 105 makes it possible to introduce a hydrogen filling into the conduit 102.
• the reactor R101 operates with a CoMo catalyst on an alumina support of the commercial reference HR626 of the company Axens.
• the operating conditions of the reactor R101 are as follows:
• FIG. 2 The diagram of FIG. 2 is implemented according to the following operating conditions:
• the fractionation in column C is ensured at a temperature of 280 ° C., so two thirds of the weight of the feed forms the heavy fraction which is sent into Z1,
• the zones of reactions Z1 and Z2 comprise CoMo catalyst on alumina support of the commercial reference HR626 of the company Axens
• the feed treated by the two processes is composed of 80% by weight of GOSR (that is to say a gas oil resulting from an atmospheric distillation) and 20% by weight of LCO. (that is, a cut from catalytic cracking).
• the filler is characterized by a density at 15 ° C of 865 kg / rrf and contains 9000 ppm by weight of sulfur and 300 ppm by weight of nitrogen.
• the feedstock arriving via line 201 is introduced into separation column C2 to produce a heavy fraction discharged through line 203 and a light fraction discharged through line 202.
• the heavy fraction circulating in line 203 is mixed with hydrogen arriving via the conduit 204 and is compressed to be introduced into the reactor R1 containing a hydrotreatment catalyst.
• the hydrotreated effluent is mixed with the light fraction circulating in the conduit 202. Then the mixture is introduced into the reactor R2 containing a hydrotreatment catalyst.
• the hydrotreated effluent from R2 is separated in the device D202 into a hydrogen-rich stream discharged through line 204 and a hydrotreated hydrocarbon stream discharged through line 205.
• FIG. 6 The diagram of FIG. 6 is implemented according to the following operating conditions:
• the reactors R1 and R2 comprise CoMo catalyst on an alumina support of the commercial reference HR626 of the company Axens
• FIG. 2 The diagram of FIG. 2 is implemented according to the following operating conditions:
• the fractionation in column C is ensured at a temperature of 280 ° C., so two thirds of the weight of the feed forms the heavy fraction which is sent into Z1,
• the zones of reactions Z1 and Z2 comprise CoMo catalyst on alumina support of the commercial reference HR626 of the company Axens
• the feedstock treated by the two processes is composed of 80% by weight of GOSR (that is to say a gas oil derived from an atmospheric distillation) and 20% by weight of LCO (that is to say cut after catalytic cracking).
• the filler is characterized by a density at 15 ° C of 865 kg / rrf and contains 9000 ppm by weight of sulfur and 300 ppm by weight of nitrogen.

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• 2013
  • 2013-11-28 FR FR1361803A patent/FR3013722B1/fr not_active Expired - Fee Related
• 2014
  • 2014-11-06 WO PCT/EP2014/073907 patent/WO2015078674A1/fr active Application Filing
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