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
  • C10G45/04—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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °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
  • C10G2300/20—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
  • C10G2300/301—Boiling range

Definitions

• the present invention relates to a catalyst comprising at least one carrier, at least one group VIII element and tungsten, and allowing the hydrodesulphurization of hydrocarbon feedstocks, preferably of the catalytic cracking (FCC) type, or catalytic cracking (FCC). fluidized bed).
• the invention relates more particularly to a process for the hydrodesulfurization of gasoline cuts in the presence of a catalyst comprising at least one support, at least one group VIII element and tungsten, in which the atomic ratio (Group VIII element) / ( group VIII + tungsten element) is greater than 0.15 and less than 0.50.
• the gasoline cuts and more particularly the gasolines from the FCC contain about 20 to 40% of olefinic compounds, 30 to 60% of aromatics and 20 to 50% of saturated paraffins or naphthenes type compounds.
• the branched olefins are in the majority with respect to linear and cyclic olefins.
• These gasolines also contain traces of highly unsaturated diolefinic compounds which can deactivate the catalysts by forming gums.
• the patent EP 685 552 B1 proposes to selectively hydrogenate the diolefins, that is to say without transforming the olefins, before carrying out the hydrotreatment for the removal of sulfur.
• the content of sulfur compounds in these species varies widely depending on the type of gasoline (steam cracker, catalytic cracking, coking, etc.) or in the case of catalytic cracking of the severity applied to the process. It can fluctuate between 200 and 5000 ppm S, preferably between 500 and 2000 ppm with respect to the mass of filler.
• the families of thiophene and benzothiophene compounds are the majority, mercaptans being present at very low levels generally between 10 and 100 ppm.
• FCC gasolines also contain nitrogen compounds in proportions generally not exceeding 100 ppm.
• the desulphurisation (hydrodesulfurization) of gasolines and mainly FCC species is therefore of obvious importance for the respect of the specifications.
• the hydrotreating (or hydrodesulphurization) of catalytic cracking gasolines when carried out under standard conditions known to those skilled in the art, makes it possible to reduce the sulfur content of the cut.
• this method has the major disadvantage of causing a very significant drop in the octane number of the cut, due to the saturation of all the olefins during the hydrotreatment. It has therefore been proposed methods for deep desulfurization of FCC gasolines while maintaining the octane number at a high level.
• the U.S. Patent 5,318,690 proposes a process of splitting the gasoline, softening the light fraction and hydrotraying the heavy fraction on a conventional catalyst and then treating it on a zeolite ZSM5 to find approximately the initial octane number.
• the request for WO 01/40409 claims the treatment of an FCC gasoline under conditions of high temperature, low pressure and high hydrogen / charge ratio. Under these particular conditions, the recombination reactions leading to mercaptan formation, involving the H 2 S formed by the desulfurization reaction and the olefins are minimized.
• Patent 5,968,346 proposes a scheme for achieving very low residual sulfur content by a multistage process: hydrodesulphurization on a first catalyst, separation of the liquid and gaseous fractions, and second hydrotreatment on a second catalyst.
• the liquid / gas separation makes it possible to eliminate the H 2 S formed in the first reactor, in order to achieve a better compromise between hydrodesulfurization and octane loss.
• the catalysts used for this type of application are sulphide catalysts containing a group VIB element (Cr, Mo, W) and a group VIII element (Fe, Ru, Os, Co, Rh , Ir, Pd, Ni, Pt). So in the US Patent 5985136 , it is claimed that a catalyst having a surface concentration of between 0.5 ⁇ 10 -4 and 3 ⁇ 10 -4 gMoO 3 / m 2 makes it possible to achieve high selectivities in hydrodesulfurization (93% hydrodesulfurization (HDS) against 33% hydrogenation of olefins (HDO)).
• HDS hydrodesulfurization
• HDO hydrogenation of olefins
• US Patent 4334982 describes a process for selective desulfurization of olefinic cuts.
• a catalyst that can be used in a gasoline hydrodesulphurization process and that makes it possible to reduce the total sulfur and mercaptan content of the hydrocarbon cuts, and preferably of FCC gasoline cuts, without any significant loss of carbon dioxide. gasoline and minimizing the decrease in the octane number.
• the invention relates more precisely to a process for the hydrodesulfurization of gasoline cuts in the presence of a catalyst comprising at least one support, at least one group VIII element and tungsten, in which the atomic ratio (group VIII element) / ( group VIII + tungsten element) is greater than or equal to 0.35 and less than 0.40.
• a catalyst comprising at least one support, at least one group VIII element and tungsten, in which the atomic ratio (group VIII element) / ( group VIII + tungsten element) is greater than or equal to 0.35 and less than 0.40.
• the charge to be hydrotreated (or hydrodesulphurized) by means of the process according to the invention is generally a petrol cut containing sulfur; such as for example a section resulting from a coking unit (coking according to the English terminology), visbreaking (visbreaking according to the English terminology), steam cracking (steam cracking according to the English terminology) or cracking catalytic (FCC, Fluid Catalytic Cracking according to the English terminology).
• Said filler preferably consists of a gasoline cut from a catalytic cracking unit whose boiling point range typically extends from the boiling points of hydrocarbons with 5 carbon atoms to about 250 ° C. vs.
• This gasoline may optionally be composed of a significant fraction of gasoline from other production processes such as atmospheric distillation (gasoline derived from a straight-run distillation or straight-run gasoline according to the English terminology). conversion (coking or steam cracking gasoline).
• the hydrodesulfurization catalysts according to the invention are catalysts comprising tungsten and at least one group VIII element on a suitable support.
• the element or elements of group VIII are preferably chosen from nickel and / or cobalt.
• the catalyst support is usually a porous solid selected from the group consisting of: aluminas, silica, silica alumina or even titanium or magnesium oxides used alone or in admixture with alumina or silica alumina.
• the support consists essentially of at least one transition alumina, that is to say that it comprises at least 51% by weight, preferably at least 60% by weight in a very preferred at least 80% by weight, or even at least 90% by weight of transition alumina. It may optionally consist solely of a transition alumina.
• the specific surface of the support according to the invention is generally less than 200 m 2 / g, preferably less than 170 m 2 / g and even more preferably less than 150 m 2 / g, or even less than 135 m 2 / g boy Wut.
• the carrier may be prepared using any precursor, method of preparation and any shaping tool known to those skilled in the art.
• the catalyst according to the invention can be prepared using any technique known to those skilled in the art, and in particular by impregnation of the elements of groups VIII and tungsten on the selected support.
• This impregnation may, for example, be carried out according to the method known to those skilled in the art in the dry-impregnation terminology, in which the quantity of desired elements in the form of soluble salts in the chosen solvent, for example demineralized water, so as to fill the porosity of the support as exactly as possible.
• the support thus filled with the solution is preferably dried.
• This treatment generally aims to transform the molecular precursors of the elements in the oxide phase. In this case it is an oxidizing treatment but a direct reduction can also be carried out.
• an oxidizing treatment also known as calcination
• this is generally carried out under air or with dilute oxygen, and the treatment temperature is generally between 200 ° C. and 550 ° C., preferably between 300 ° C. C and 500 ° C.
• a reducing treatment this is generally carried out under pure hydrogen or preferably diluted, and the treatment temperature is generally between 200 ° C. and 600 ° C., preferably between 300 ° C. and 500 ° C.
• Salts of group VIII and tungsten elements which can be used in the process according to the invention are, for example, cobalt nitrate, aluminum nitrate or ammonium metatungstate. Any other salt known to those skilled in the art having sufficient and decomposable solubility during the activation treatment may also be used.
• the catalyst is usually used in a sulfurized form obtained after treatment in temperature in contact with a decomposable organic sulfur compound and generating H 2 S or directly in contact with a gas stream of H 2 S diluted in H 2 .
• This step may be carried out in situ or ex situ (inside or outside the reactor) of the hydrodesulfurization reactor at temperatures between 200 and 600 ° C and more preferably between 300 and 500 ° C.
• the use of large specific surface support is sometimes problematic in the case of strongly olefinic feeds. Indeed, as the surface acidity increases with the specific surface of the supports, the acid-catalysed reactions will be favored for the supports of important specific surface. Thus, the polymerization or coking reactions leading to the formation of gums or coke and finally to the premature deactivation of the catalyst will in this case be greater on high specific surface supports. A better stability of the catalysts will then be obtained for small specific surface supports.
• the specific surface of the support should preferably not exceed about 300 m 2 / g and should more preferably be less than 280 m 2 / g, or even less than 150 m 2 / g.
• the content of group VIII elements of the catalyst according to the invention is preferably between 1% by weight and 20% by weight of Group VIII element oxides, preferably between 2% by weight and 8% by weight of oxides of Group VIII elements. elements of group VIII.
• the group VIII element is cobalt or nickel or a mixture of these two elements, and more preferably the group VIII element consists solely of cobalt and / or nickel.
• the tungsten content is preferably between 1.5% by weight and 60% by weight of tungsten oxide, more preferably between 3% by weight and 50% by weight of tungsten oxide.
• the atomic ratio (group VIII element) / (group VIII + tungsten element) is greater than or equal to 0.35 and less than or equal to 0.40.
• the catalyst according to the invention can be used in any process known to those skilled in the art, for desulfurizing hydrocarbon cuts of the type of catalytic cracking gasoline (FCC) for example by maintaining the octane number at high values. . It can be used in any type of reactor operated in fixed bed or mobile bed or bubbling bed, it is however preferably used in a reactor operated in fixed bed.
• FCC catalytic cracking gasoline
• the operating conditions allowing selective hydrodesulphurization of the catalytic cracking gasolines are a temperature of between 200 ° C. and 400 ° C., preferably between 250 ° C. and 350 ° C., a total pressure of between 1 MPa and 3 MPa and more preferably between about 1 MPa and about 2.5 MPa with a ratio: volume of hydrogen per volume of hydrocarbon feed, of between 100 and 600 liters per liter and more preferably between about 200 and about 400 liters per liter.
• the hourly volume velocities (VVH) are between 1 and 15 h -1 .
• the VVH is defined by the ratio of the volume flow rate of the liquid hydrocarbon feedstock by the volume of catalyst charged to the reactor.
• the molybdenum catalyst A is prepared by adding cobalt and molybdenum to an alumina support which is in the "ball" form. These two elements are introduced simultaneously by dry impregnation of the support.
• the cobalt salt used is cobalt nitrate, the molybdenum precursor being ammonium heptamolybdate tetrahydrate.
• Catalyst A The characteristics of Catalyst A are given in Table 1 below: ⁇ b> Table 1.: ⁇ / b> characteristics of Catalyst A (non-compliant). Support S BET of support m 2 / g Surface density CoO mole / m 2 Surface density MoO 3 mole / m 2 Co / (Co + Mo) SCM139XL 135 3.56.10 -6 6,40.10 -6 0.36
• Catalyst B (non-compliant):
• the molybdenum catalyst B is prepared in the same manner as the catalyst A, with a high surface area alumina to decrease the surface density of the molybdenum oxide.
• the characteristics of catalyst B are provided in Table 2 below. ⁇ b> Table 2.: ⁇ / b> characteristics of catalyst B (non-compliant).
• Tungsten catalyst C is prepared by adding cobalt and tungsten to an alumina support in the form of a ball. Both elements are introduced simultaneously by dry impregnation of the support.
• the cobalt salt employed is Co nitrate, the precursor of tungsten being ammonium metatungstate.
• the characteristics of catalyst C are given in Table 3 below. ⁇ b> Table 3 ⁇ / b>.
• Support S BEF support m 2 / g Surface density CoO mole / m 2 Surface density WO 3 mole / m 2 Co / (Co + W) SCM139XL 135 3,88.10 -6 6,21.10 -6 0.38
• the tungsten catalyst D is prepared in the same manner as the catalyst C, with a high surface area alumina to decrease the surface density of the tungsten oxide.
• the characteristics of catalyst D are provided in Table 4 below. ⁇ b> Table 4.: ⁇ / b> characteristics of catalyst D (compliant).
• Catalyst E is prepared in the same manner as catalyst C.
• the surface density of tungsten oxide is identical to that of catalyst C (conforming), while that of cobalt is reduced.
• the characteristics of catalyst E are provided in the table below. ⁇ b> Table 5 ⁇ / b>. : characteristics of catalyst E (non-compliant).
• Catalyst F is prepared in the same way as catalyst C.
• the surface density of tungsten oxide is identical to that of catalyst C (compliant). while that of cobalt is diminished.
• the characteristics of the catalyst F are given in the table below. ⁇ b> Table 6 ⁇ / b>. : characteristics of the catalyst F (compliant).
• Catalyst G is prepared in the same way as catalyst C.
• the surface density of tungsten oxide is identical to that of catalyst C (conforming), while that of cobalt is reduced.
• the characteristics of the catalyst G are given in the table below. ⁇ b> Table 7 ⁇ / b>. : characteristics of catalyst G (compliant).
• Catalyst H is prepared in the same manner as catalyst C.
• the surface density of tungsten oxide is identical to that of catalyst C (conforming), while that of cobalt is increased.
• the characteristics of the catalyst H are given in the table below. ⁇ b> Table 8 ⁇ / b>. : characteristics of the catalyst H (compliant).
• Catalyst I is prepared in the same way as catalyst C.
• the surface density of tungsten oxide is identical to that of catalyst C (conforming), while that of cobalt is increased.
• the characteristics of catalyst I are provided in the table below. ⁇ b> Table 8 ⁇ / b>. : characteristics of catalyst I (non-compliant).
• the catalyst Before testing, the catalyst is previously sulphurized in a sulfurization bench, under a H 2 S / H 2 mixture (41 g / h, 15% vol H 2 S) at 500 ° C. for two hours (ramp of 5 ° C./min) and then reduced under pure H 2 at 200 ° C for two hours. The catalyst is then transferred to the Grignard reactor in the absence of air. The tests are continued until the levels of HDS (conversion of methyl-3 thiophene) close to 90%.
• H 2 S / H 2 mixture 41 g / h, 15% vol H 2 S
• HDS conversion of methyl-3 thiophene
• the rate constant (normalized per g of catalyst) is calculated by considering an order 1 for the desulfurization reaction (k HDS ), and an order 0 for the hydrogenation reaction (k HDO ).
• the selectivity of a catalyst is defined by the ratio of its speed constants, k HDS / k HDO ).
• the relative rate constants with respect to catalyst A, catalysts A, B, C and D and their selectivity are reported in Table 9 below.
• tungsten catalysts are more selective, at iso-surface density, than molybdenum-based catalysts. ⁇ b> Table 9 ⁇ / b>.
• Catalytic properties of catalysts A, B, C and D are reported in Table 9 below.
• Catalyst k HDS k HDO kHDS / kHDO Co / Co + (W or Mo) Surface density MoO 3 or WO 3 mole / m 2 A (MB) 1.00 1.62 0.62 0.36 6,40.10 -6 B (MB) 1.26 2.29 0.55 0.40 4.60.10 -6 C (W) 0.75 1.05 0.71 0.38 6,21.10 -6 D (W) 1.07 1.67 0.64 0.40 4.66-10 -6
• the catalysts C, E, F, G, H, I are tested on a model charge, according to the same protocol as described in Example 1.
• the relative rate constants of the catalysts and their selectivity are reported in Table 10 below. below. ⁇ b> Table 10 ⁇ / b>. : Catalytic properties of catalysts C, E, F, G, H, I.
• Catalyst E sees its selectivity greatly decrease for a Co / (Co + W) ratio of 0.10. In the same way, the catalyst I having a ratio Co / (Co + W) that is too high (0.53) decreases its selectivity.

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• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 2002
  • 2002-06-03 FR FR0206816A patent/FR2840316B1/fr not_active Expired - Lifetime
• 2003
  • 2003-05-14 EP EP03291116.6A patent/EP1369467B1/fr not_active Expired - Fee Related
  • 2003-06-02 US US10/449,725 patent/US7223333B2/en not_active Expired - Fee Related
  • 2003-06-03 JP JP2003158147A patent/JP2004010893A/ja active Pending
  • 2003-06-03 CN CN2011102617021A patent/CN102358845A/zh active Pending
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