Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F7/00—Compounds of aluminium
  • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
  • C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
  • C01F7/447—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by wet processes
  • C01F7/448—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by wet processes using superatmospheric pressure, e.g. hydrothermal conversion of gibbsite into boehmite
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
  • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/883—Molybdenum and nickel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/31—Density
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/635—0.5-1.0 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/66—Pore distribution
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/15—X-ray diffraction
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/04—Compounds with a limited amount of crystallinty, e.g. as indicated by a crystallinity index
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/14—Pore volume
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/16—Pore diameter

Definitions

• the present invention relates to new alumina-based extrudates. It also relates to processes for the preparation of these extrudates and their use as catalyst supports, in particular for hydrotreatment.
• Hydrotreating of petroleum fractions is a hydrogen pressure purification operation covering several types of treatment and in particular: hydrodesulfurization, hydrodemetallization, hydrodenitrification, conradson carbon hydroreduction (HDCC), hydrogenation asphaltenes (HDAS), hydrogenation of aromatics (HDAr).
• Hydrodemetallization allows the elimination of metals, nickel and vanadium in particular, contained in heavy petroleum fractions resulting from vacuum distillations of the first stages of the refinery.
• Hydrodesulfurization allows the elimination of sulfur compounds such as RSH or R 2 S, R being an alkyl radical. It is rather used on light petroleum fractions or with a low metal content (Ni and V).
• the catalyst must have a good retention capacity in hydrodemetallization.
• the reaction products of which remain in the reaction medium the products from hydrodemetallization remain absorbed on the catalyst. It is therefore important that the catalyst can absorb the greatest possible amount of metal derivatives from hydrodemetallization because once saturated with metal derivatives, it will have to be replaced.
• a first problem is due to the fact that the metal compounds are molecules of high molecular weight, such as asphaltenes and resins, having a large steric hindrance, hence diffusional limitations in the network of pores of the catalyst.
• a second problem is that the metals or more precisely the sulphides of the metals resulting from the decomposition of the metal compounds accumulate during the operation gradually decreasing the diameter of the pores.
• a third problem is related to the fact that the metal compounds, of the asphaltenes type, tend under operating conditions to dehydrogenate then to polycondense to give rise to products insoluble in the hydrocarbon medium and to coke which remains fixed on the catalyst whose activity it gradually decreases.
• a heavy-cut hydrotreating catalyst must therefore be composed of a catalytic support having a porosity profile which is particularly suited to the diffusion constraints specific to hydrotreatments and in particular to hydrodemetallization.
• the catalysts usually used are composed of a support on which metal oxides are deposited, such as for example the oxides of cobalt, nickel or molybdenum.
• the support is generally based on alumina, its role being to disperse the active phase and to present a texture suitable for good capture of metallic impurities while avoiding the problems defined above.
• alumina supports of the prior art There are two types of alumina supports of the prior art. First, there are alumina extrudates prepared from gel alumina.
• the process for preparing gel alumina is particularly polluting, unlike that of alumina resulting from the rapid dehydration of hydrargillite, called flash alumina.
• alumina beads prepared on the basis of alumina resulting from the rapid dehydration of hydrargillite, the cost of which is lower.
• these balls have a drawback: in order to present a cost price satisfactory, the diameter of the balls is greater than 2 mm so that the metals cannot enter the core of the balls. The catalytic phase with which the core of the beads is impregnated is therefore not used.
• An objective of the present invention to provide supports based on alumina for hydrotreatment whose cost is low.
• Another objective of the present invention is to provide alumina extrudates, resulting from the rapid dehydration of hydrargillite, the characteristics of which are suitable for their use as catalyst supports for hydrotreatment.
• Another object of the present invention is to provide processes for the preparation of these alumina extrudates.
• the invention firstly relates to alumina extrudates originating from a preparation process starting from an alumina resulting from the rapid dehydration of hydrargillite having a total pore volume of at least 0.6 cm 3 / g, an average mesoporous diameter between 140 and 360 ⁇ , an alumina content resulting from the decomposition of boehmite between 5 and 70% by weight.
• the invention also relates to a first process for forming alumina from a starting alumina resulting from the rapid dehydration of hydrargillite, comprising the following steps: a-
• the starting alumina is rehydrated, d.
• the rehydrated alumina is kneaded in the presence of an emulsion of at least one hydrocarbon in water, d j .
• the extrudates are dried and calcined, fj.
• the extrudates from step e ⁇ are subjected to an acid hydrothermal treatment in a confined atmosphere, g-
• the invention also relates to a second process for forming alumina from a starting alumina resulting from the rapid dehydration of hydrargillite, comprising the following steps: a 2 . we start with a starting alumina from the rapid dehydration of hydrargillite, b 2 . the alumina is shaped in the form of beads in the presence of a pore-forming agent,
• the alumina beads obtained are ripened, d 2 .
• the beads from step c 2 are kneaded, whereby a paste is obtained which is extruded, e 2 .
• the extrudates obtained are dried and calcined, f 2 .
• the extrudates from step e 2 are subjected to an acid hydrothermal treatment in a confined atmosphere, g 2 . optionally drying, and calcining the extrudates from step f 2 .
• the invention also relates to a third method for forming alumina from a starting alumina resulting from the rapid dehydration of hydrargillite, comprising the following steps: a 3 .
• the starting alumina, c 3 is rehydrated.
• the rehydrated alumina is kneaded with a pseudo-boehmite gel, said gel being present in a content of between 1 and 30% by weight relative to the rehydrated alumina and to the gel, d 3 .
• the alumina paste obtained in step c 3 , e 3 is extruded.
• the extrudates are dried and calcined, f 3 .
• the extrudates from step e 3 are subjected to an acid hydrothermal treatment in a confined atmosphere, g 3 . optionally drying, and calcining the extrudates from step f 3 .
• the invention relates to the use of this alumina as a catalyst or catalyst support.
• Figures 1 and 2 are photographs of sections of an extrusion according to the invention made by transmission electron microscopy.
• the extrudates according to the invention have the advantage of being balanced in hydrodemetallization and hydrodesulfurization and in having a good retention capacity in hydrodemetallization.
• the invention relates first of all to alumina extrudates from a preparation process starting from an alumina resulting from the rapid dehydration of hydrargillite having a total pore volume of at least 0.6 cm 3 / g, an average mesoporous diameter between 140 and 360 A, an alumina content resulting from the decomposition of boehmite between 5 and 70% by weight.
• alumina resulting from the decomposition of boehmite it should be understood that during the process for preparing the extrudates, alumina of the boehmite type developed to the point of representing 5 to 70% by weight of the total alumina, then has been broken down. This level of alumina resulting from the decomposition of boehmite is measured by X-ray diffraction on the alumina before decomposition of said boehmite.
• the alumina extrudates according to the invention have a total pore volume (VPT) of at least 0.6 cm 3 / g, preferably at least 0.65 cm 3 / g.
• VPT is measured as follows: the value of the grain density and of the absolute density is determined: the grain densities (Dg) and absolute (Da) are measured by the picnometry method with mercury and helium, VPT is given by the formula:
• the extrudates according to the invention also have an average mesoporous diameter of between 150 and 360 A.
• the average mesoporous diameter for given extrudates is measured on the basis of the graphic representation of the porous distribution of said extrudates. This is the diameter whose associated volume on the graphic representation is worth:
• V-iooo ⁇ representing the volume created by pores with a diameter greater than 1000 ⁇ or macroporous volume.
• V-ioco ⁇ representing the mesoporous volume ie the volume created by pores with a diameter between 60 ⁇ and 1000 ⁇ , that is to say the volume created by all pores with a size between 60 ⁇ and 1000 ⁇
• the extrudates according to the invention have a mesoporous volume ( V 60 ⁇ " V 1000 ⁇ ) of at least 0.3 cm 3 / g, or even at least 0.5 cm 3 / g.
• the extrudates according to the invention have a macroporous volume 0 / IOOO ⁇ ) of at most 0.5 cm 3 / g.
• the macroporous volume (V 10 OO ⁇ ) is at most 0.3 cm 3 / g, even more preferably at most 0.1 cm 3 / g, or even at most 0.08 cm 3 / g.
• these extrudates have a microporous volume (V 0 -6o ⁇ ) of at most 0.55 cm 3 / g, preferably at most 0.2 cm 3 / g.
• the microporous volume represents the volume created by the pores of diameter less than 60 ⁇ .
• Such a porous distribution which minimizes the proportion of pores less than 60 ⁇ and those greater than 1000 ⁇ while increasing the proportion of mesopores (diameter between 60 ⁇ and 1000 ⁇ ) is particularly suited to the diffusional constraints of the hydrotreating of hydrocarbon slabs heavy.
• the porous distribution over the range of pore diameter between 60 ⁇ and 1000 ⁇ is extremely tight around the pore diameter 140 ⁇ , preferably on said range the majority of pores have a diameter between 60 and 500 ⁇ , even more preferably between 80 and 200 ⁇ .
• the extrudates according to the invention can have a specific surface (SS) of at least 120 m 2 / g, preferably at least 150 m 2 / g.
• This surface is a BET surface.
• BET surface is understood to mean the specific surface determined by nitrogen adsorption in accordance with standard ASTM D 3663-78 established on the basis of the BRUNAUER - EMMETT - TELLER method described in the periodical "The Journal of the American Society", fi ⁇ , 309 (1938).
• the extrudates according to the invention are preferred, the diameter of which is between 0.3 and 10 mm, preferably between 0.8 and 3.2, and the length of which is between 1 and 20 mm, preferably between 1 and 10.
• extrudates generally have a grain-to-grain crushing (EGG) of at least 0.7 kg / mm for extrudates with a diameter of 1.6 mm, preferably at least 1, and a crush resistance (ESH) ) at least 1 MPa.
• the grain-to-grain crushing method (EGG) consists of measuring the maximum form of compression that an extrusion can withstand before it breaks, when the product is placed between two planes moving at a constant speed of 5 cm / min .
• grain-to-grain crushing is expressed as the ratio of force to length of the generator of the extruded.
• the crush resistance measurement method (ESH) consists in subjecting a certain quantity of extrudates to an increasing pressure above a sieve and recover the fines from the crushing of the extrudates.
• the crush resistance corresponds to the force exerted to obtain a level of fines representing 0.5% of the weight of the extrudates subjected to the test.
• the alumina according to the invention is present on a microscopic scale partly in the form of stacks of sheets and partly in the form of needles, said needles being dispersed both around the stacks of sheets and between the sheets .
• the length and width of the sheets varies between 1 and 5 ⁇ m and their thickness is of the order of 10 nm. They can be stacked in groups forming a thickness of the order of 0.1 to 0.5 ⁇ m, the groups being able to be separated from each other by thickness of the order of 0.05 to 0.1 ⁇ m.
• the length of the needles can be between 0.05 and 0.5 ⁇ m; their section is of the order of 5 to 20 nm. These measurements are given by measurement on the photos of the extrudates taken with the electron microscope.
• the needles between the sheets are generally smaller than the needles around the sheets.
• the alumina sheets mainly include um alumina and ⁇ alumina and the ⁇ alumina needles.
• the structure in sheets is characteristic of the hydrargillite filiation of alumina, which means that these extrudates before activation by calcination presented this same structure, the sheets being of hydrargillite nature.
• this alumina in hydrargillite form is mainly transformed into dehydrated aluminas ⁇ and ⁇ .
• the needle structure is characteristic of boehmite parentage, which means that these extrudates before activation by calcination had this same structure, the needles being of boehmite nature. Then, by calcination, this alumina in boehmite form is transformed into dehydrated ⁇ alumina.
• extrudates according to the invention are therefore obtained by calcination, the extrudates before calcination consisting of sheets based on hydrargillite alumina; these sheets are surrounded at the periphery of the needles based on boehmite alumina, such needles are also found between the sheets.
• the invention also relates to a first method of forming such an alumina from a starting alumina resulting from the rapid dehydration of hydrargillite, characterized in that it comprises the following steps: a-
• the alumina paste obtained in step cj is extruded, e ⁇ the extrudates are dried and calcined, fi- subjecting the extrudates from step e 1 to an acid hydrothermal treatment in a confined atmosphere, g ⁇ optionally drying, and the extrudates from step f ⁇ are calcined .
• the shaping process according to the invention is suitable for a specific starting alumina resulting from the rapid dehydration of Bayer hydrate (hydrargillite) which is an easily accessible and very inexpensive industrial aluminum hydroxide.
• Such an alumina is in particular obtained by rapid dehydration of hydrargillite using a stream of hot gases, the inlet temperature of the gases into the apparatus generally varying from approximately 400 to 1,200 ° C., the contact time of the alumina with the hot gases generally being between a fraction of a second and 4-5 seconds; such a process for preparing alumina powder has been particularly described in patent FR-A-1 108 011.
• the alumina thus obtained can be used as it is or can undergo before step b- ) a treatment to remove in particular the alkalis present: an Na 2 O content of less than 0.5% by weight may be preferred.
• step b this starting alumina, which is in the form of a powder, is rehydrated. This rehydration leads to the transformation of the alumina into a rehydrated alumina partly in the form of alumina type boehmite of particular texture.
• the starting alumina is rehydrated so that it has a boehmite type alumina content of at least 3% by weight, even more preferably at most 40% by weight, in particular between 10 and 35%.
• This rehydration can be carried out by any means known to those skilled in the art.
• the starting alumina is rehydrated by suspension in water in the presence of a complexing agent of the cation Al 3+ .
• This complexing agent can be chosen from the group formed by: - acids comprising at least one carboxylate group and at least two hydroxyl and / or amino groups, or comprising at least two carboxylate groups and at least one hydroxyl and / or amino group, and their salts, the organic phosphoric acids of formulas (I), (II) and (III) below
• n and m are whole numbers between 1 and 6
• p is an integer between 0 and 5
• R1, R2, R3 identical or different representing a hydrogen atom, an aralkyl, aryl, alkyl or a hydroxyl or amino group
• R represents a hydrogen atom, a hydrocarbon radical having from 1 to 20 carbon atoms or a halogen atom.
• this complexing agent is a carboxylic acid having from 2 to 15 carbon atoms. It can in particular be chosen from:
• - hydroxypolycarboxylic acids and more particularly, - hydroxydi- or hydroxytricarboxylic acids such as malic acid, citric acid or tartronic acid,
• the salts of these acids are also suitable for the invention, such as the alkali metal, in particular sodium, salts and the ammonium salts.
• an organic phosphoric acid preferably aliphatic, substituted or not. This comprises 1 to 15 carbon atoms, preferably 1 to 10.
• organic phosphoric acid preferably aliphatic, substituted or not.
• a compound corresponding to formula (IV) is preferably chosen in which R is a hydrogen atom or a linear or branched, saturated or unsaturated aliphatic group, having preferably from 5 to 20 carbon atoms.
• Toxin (8-hydroxy-quinoline) or an 8-hydroxyquinoline of formula (IV) in which R is always a hydrogen atom, with the exception of position 7 on the cycle where it represents an alkyl group of formula C m H 2m + ⁇ with m between 5 and 20.
• the complexing agent as defined is used in solid form or preferably in the form of an aqueous solution, the concentration of which preferably varies between 0.01 and 1 mole / liter.
• the amount of complexing agent introduced relative to the amount of alumina is determined such that it preferably represents between 0.01 and 5% of the weight of alumina, and even more preferably between 0.05 and 1%.
• the preferred complexing agent is citric acid. It can be used at a content of between 0.1 and 1% by weight relative to the alumina.
• the suspension of alumina in the presence of the complexing agent of the cation Al 3+ is generally carried out at a concentration of between 200 and 700 g / l of alumina in water, preferably at 500 g / l.
• can vary between 50 and 100 ° C for a period between a few hours and 72 hours.
• the alumina suspended is then filtered, a cake is recovered which can be washed with water.
• the rehydrated alumina is then subjected, in step c- (, to kneading in the presence of an emulsion of at least one hydrocarbon in water.
• drying the rehydrated alumina from step b-j It is possible, between the steps -
• This drying must be carried out under conditions making it possible to remove the water which is impregnated with the rehydrated alumina but without eliminating the water bound to the alumina, therefore the drying temperature is at most 250 ° C.
• the cake is dried so that the dried alumina powder has a loss on ignition measured by calcination at 1000 ° C of between 20 and 40%.
• step c- ( ) the rehydrated alumina is kneaded with an emulsion of at least one hydrocarbon in water.
• This emulsion is obtained by mixing in water the hydrocarbon and a surfactant -active.
• This hydrocarbon can be chosen from those having a number of carbon atoms between 10 and 15 and a boiling temperature between 185 and 200 ° C such as for example kerosene, paraffin oil or any other cut. alkanes, and mixtures thereof.
• the emulsion may have an aqueous phase / hydrocarbon weight ratio of at least 1.
• the amount of hydrocarbon, in emulsion in water, kneaded with the rehydrated alumina is generally at least 5% by weight relative to the weight of the rehydrated alumina, preferably at least 10% and d '' at most 50%.
• the petroleum emulsion in water comprises a nonionic surfactant.
• these are nonionic surfactants having ethylene oxide (EO) - propylene oxide (OP) di-blocks, in particular those having a number of OP units of at least 10.
• the surfactant is chosen from those for which the hydrocarbon emulsion in water is stable in an acid medium.
• an emulsion as defined above is prepared by mixing and stirring water, a hydrocarbon and the surfactant to be tested, then an acid is added thereto. If, we observe a settling phenomenon by separation of the three phases water / surfactant / hydrocarbon, the emulsion is not stable in an acid medium.
• Galoryl EM 10® from the Compagnie für Produits Industriels, Soprophor SC138® marketed by Rhône-Poulenc Geronazzo.
• the content of surfactant in the emulsion is at least 3% by weight relative to the hydrocarbon, preferably between 5 and 15%.
• the emulsion is generally prepared by bringing the various constituents into contact (water, hydrocarbons, surfactants) then stirring.
• the rehydrated alumina and the emulsion are mixed in an acid medium, in particular in the presence of nitric acid.
• the acid can be introduced via the emulsion.
• the mixing can be carried out by any manner known to those skilled in the art, and in particular using a Z-arm mixer or a twin-screw mixer. Water can be added to adjust the viscosity of the dough to be extruded.
• the kneading is carried out in an acid medium, it is preferable to neutralize the alumina-based paste between steps c-
• This neutralization can be carried out using an ammonia-type base.
• the neutralizer is usually introduced at the end of mixing.
• step d- j the dough from the kneading is extruded through a die, for example using a piston or a double extrusion screw.
• This extrusion step can be carried out by any method known to those skilled in the art.
• the alumina extrudates are dried and calcined.
• the drying temperature can be between 100 and 200 ° C, the calcination temperature between 200 and 700 ° C.
• step f j The extrudates from stage e-
• Hydrothermal treatment in a confined atmosphere is understood to mean treatment by autoclaving in the presence of water at a temperature above ambient temperature.
• the shaped alumina can be treated in different ways.
• the alumina can be impregnated with acid, before it is autoclaved, the autoclaving of the alumina being done either in the vapor phase or in the liquid phase, this vapor or liquid phase of the autoclave being able to be acidic or not.
• This impregnation prior to autoclaving, can be carried out dry or by immersion of alumina in an acidic aqueous solution.
• dry impregnation oh means bringing the alumina into contact with a volume of solution less than or equal to the total pore volume of the treated alumina.
• the impregnation is carried out dry.
• the agglomerates can also be treated without prior impregnation with an acid, the acidity being in this case provided by the aqueous liquid of the autoclave.
• the hydrothermal treatment is usually carried out in the presence of an acidic aqueous solution consisting of a mixture of at least one acid making it possible to dissolve at least part of the alumina from extrudates and at least one compound providing an anion capable of combine with aluminum ions in solution.
• an acidic aqueous solution consisting of a mixture of at least one acid making it possible to dissolve at least part of the alumina from extrudates and at least one compound providing an anion capable of combine with aluminum ions in solution.
• the acid should preferably dissolve at least 0.5% by weight of alumina from the alumina extrudates.
• this acid is chosen from strong acids such as: nitric acid, hydrochloric acid, perchloric acid, sulfuric acid or a weak acid used at a concentration such that its aqueous solution has a pH below 4, such as acetic acid, or a mixture of these acids.
• strong acids such as: nitric acid, hydrochloric acid, perchloric acid, sulfuric acid or a weak acid used at a concentration such that its aqueous solution has a pH below 4, such as acetic acid, or a mixture of these acids.
• compound providing an anion capable of combining with aluminum ions in solution means any compound capable of releasing an anion A _n in solution capable of forming, with the Al 3+ cations, products in which the ratio
• salts can be illustrated by the basic salts of general formula AI 2 (OH) x A y in which 0 ⁇ x ⁇ 6; ny ⁇ 6; n represents the number of charges of the anion A.
• the compounds capable of releasing in solution the anions chosen from the group consisting of the nitrate, chloride, sulfate, perchlorate, chloroacetate, dichloracetate, trichloracetate, bromoacetate, dibromoacetate anions and the anions of general formula:
• the anions capable of liberating the anion A _n in solution can effect this liberation, either directly by dissociation, or indirectly, for example by hydrolysis.
• the compounds can in particular be chosen from the groups comprising: mineral or organic acids, anhydrides, organic or mineral salts, esters.
• the salts there may be mentioned the alkaline or alkaline earth salts soluble in an aqueous medium, such as those of sodium, potassium, magnesium or calcium, ammonium salts, aluminum salts, rare earth salts.
• the hydrothermal treatment is carried out in the presence of a mixture of nitric acid and acetic acid.
• the respective amounts of these two acids are generally between 3 and 15% by weight.
• the autoclave is preferably an autoclave with a rotating basket such as that defined in patent application EP-A-0 387 109.
• the temperature during autoclaving can be between 150 and 250 ° C for a period of time between 30 minutes and 3 hours.
• the treatment can be carried out under saturated vapor pressure or under a partial vapor pressure of water at least equal to 70% of the saturated vapor pressure corresponding to the treatment temperature.
• This hydrothermal treatment in a confined atmosphere leads to the transformation of at least part of the alumina in the form of boehmite.
• the hydrothermal treatment must be carried out in such a way that, at the end of step f 1 (the alumina has a boehmite type alumina content of at most 70% by weight, preferably at least 5% Those skilled in the art know how to adjust the autoclaving parameters allowing such rates to be obtained.
• the extrudates are optionally dried, then calcined (step g ⁇ .
• the drying temperature can be between 100 and 200 ° C and the calcination temperature between 200 and 700 ° C.
• the invention also relates to a second process for forming an alumina, as described above, from a starting alumina resulting from the rapid dehydration of hydrargillite as described above, characterized in that it comprises the following steps:
• alumina o part of a starting alumina resulting from the rapid dehydration of hydrargillite, b 2 .
• the alumina is shaped in the form of beads in the presence of a pore-forming agent, c 2 .
• the alumina beads obtained are ripened, d 2 .
• the beads from step c 2 are kneaded, whereby a paste is obtained which is extruded, e 2 .
• the extrudates obtained are dried and calcined, f.
• the extrudates from step e 2 are subjected to an hydrothermal acid treatment in a confined atmosphere, g 2 . optionally drying, and calcining the extrudates from step f 2 .
• This second shaping process according to the invention is also suitable for a specific starting alumina resulting from the rapid dehydration of Bayer hydrate.
• the alumina is shaped in the form of beads.
• This shaping can be carried out by any technique known to those skilled in the art. It is carried out directly on the alumina powder by rotating technology.
• Rotating technology is understood to mean any device in which agglomeration is carried out by bringing the product to be granulated into contact and rotating on itself.
• This shaping is carried out in the presence of a pore-forming agent.
• pore-forming compounds used there may be mentioned, by way of example, wood flour, charcoal, sulfur, tars, plastics or plastic emulsions such as polyvinyl chloride, polyvinyl alcohols, mothballs or the like, and generally all organic compounds capable of being removed by calcination.
• the amount of pore-forming compounds added is not critical, nor is their size. In general, the amount of porogens is between 5 and 30% by weight relative to the alumina.
• the size of the beads obtained is not critical. They are generally between 1 and 5 mm.
• step c 2 The beads from step b 2 are then subjected to ripening.
• This ripening is achieved by maintaining the alumina beads in an atmosphere with controlled humidity.
• the temperature can be between 30 and 100 ° C, preferably between 80 and 100 ° C.
• the duration of ripening can vary between a few hours and a few tens of hours, preferably between 6 and 24 hours.
• the alumina rehydrates into boehmite (AI 2 O 3 , H 2 O) and bayerite (AI 2 O 3 , 3H 2 O).
• the boehmite-type alumina level is preferably between 5 and 40%, preferably between 20 and 30% relative to the weight of the alumina.
• One practical embodiment of ripening consists in injecting living water vapor onto the alumina beads.
• the ripened alumina beads are kneaded in the presence of water and acid so as to break them and obtain a homogeneous extrudable paste.
• the acid used can be a strong acid (nitric acid for example) or acetic, formic acid, etc.
• the amount of acid relative to the alumina is generally between 0.5 and 15% by weight.
• the mixing can be carried out by any manner known to those skilled in the art, and in particular using a Z-arm mixer or a twin-screw mixer.
• This paste is then extruded through a die, for example using a piston or a continuous twin screw or single screw extruder.
• This extrusion step can be carried out by any method known to those skilled in the art.
• the viscosity of the dough to be extruded is adjusted by the amount of water added during mixing.
• the extrudates are dried and calcined.
• the drying temperature can be between 100 and 200 ° C as before, the calcination temperature between 200 and 800 ° C.
• step f The extrudates from step e 2 are then subjected to an acid hydrothermal treatment in a confined atmosphere (step f).
• the hydrotreatment conditions are identical to those defined for the first preparation process described above.
• the extrudates are optionally dried, then calcined (step g 2 ).
• the drying temperature can be, as for the first process, between 100 and 200 ° C and the calcination temperature between 200 and 700 ° C.
• the invention also relates to a third process for forming an alumina, as described above, from a starting alumina resulting from the rapid dehydration of hydrargillite as described above, characterized in that it comprises the following steps: a 3 . we start with an alumina from the rapid dehydration of hydrargillite b 3 . the starting alumina, c 3 , is rehydrated. the rehydrated alumina is kneaded with a pseudo-boehmite gel, said gel being present in a content of between 1 and 30% by weight relative to the rehydrated alumina and to the gel, d 3 . the alumina paste obtained in step c 3 , e 3 is extruded.
• the extrudates are dried and calcined, f 3 .
• the extrudates from step e 3 are subjected to an acid hydrothermal treatment in a confined atmosphere, g 3 . optionally drying, and calcining the extrudates from step f 3 .
• step c 3 the rehydrated alumina resulting from step b 3 is kneaded not with a hydrocarbon emulsion, but with a pseudo-boehmite gel in a content of between 1 and 30% by weight relative to the rehydrated alumina and to the gel, preferably between 5 and 20% by weight.
• Such a pseudo-boehmite gel can be obtained by precipitation of aluminum salts such as aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum acetate with a base or by hydrolysis of aluminum alkoxides such as aluminum triethoxide.
• aluminum salts such as aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum acetate with a base
• aluminum alkoxides such as aluminum triethoxide.
• the mixing can be carried out by any manner known to those skilled in the art, and in particular using a Z-arm mixer or a twin-screw mixer.
• Water can be added to adjust the viscosity of the dough to be extruded.
• the invention relates to the use of the alumina extrudates previously described or derived from the above processes as catalysts, catalyst supports or adsorbents.
• FIG. 2 a sheet is again observed separated from the other sheets by needles.
• the scale of the photograph is such that 1 cm in the photo represents 79 nm in reality.
• the product obtained consists of transition aluminas: alumina ⁇ (vic) and ⁇ (rho).
• the specific surface is 300 m / g and the loss on ignition (PAF) of 5%.
• Step b j - Rehydration - The alumina is subjected to rehydration by suspension in water at a concentration of 500 g / l at a temperature of 90 ° C for a period of 48 h in the presence of 0.5% citric acid.
• the alumina obtained is in powder form, its loss on ignition (PAF), measured by calcination at 1000 ° C., and its level of alumina in boehmite form, measured by X-ray diffraction, are collated in Table 1.
• Step c- - Mixing - 10 kg of the rehydrated and dried powder are introduced into a Z-arm mixer of volume 25 I, then little by little a hydrocarbon emulsion in water stabilized by a surfactant, previously obtained in a stirred reactor, and 69% nitric acid. The characteristics are collated in Table 1. The mixing is extended until a consistent, homogeneous paste is obtained.
• Step d- - Extrusion -
• the paste obtained is introduced into a single-screw extruder to obtain raw extrudates with a diameter of 1.6 mm.
• Step e- - Drying / calci nation -
• the extrudates are then dried at 140 ° C for 15 h and calcined for 2 h at a temperature indicated in Table 1.
• the support thus calcined has a specific surface adjustable between 200 m 2 / g and 130 m 2 / g as shown in Table 1.
• Step ⁇ - Hydrothermal treatment The extrudates obtained are impregnated with a solution of nitric acid and acetic acid in the following concentrations: 3.5
• Step g- ⁇ - Drying / calcination - At the end of this treatment, the extrudates are subjected to calcination at a temperature of 550 ° C. for 2 h.
• the characteristics of the extrudates obtained are collated in Table 1.
• the boehmite level is measured on the extrudates before final calcination.
• Example 1 The same steps are implemented as in Example 1 except that the kneading step d is implemented in the following manner.
• Step c-) - Mixing - This is a continuous process in a corrosive twin-screw mixer. Upstream of the mixer, the rehydrated and dried powder is introduced at a rate of
• an emulsion of petroleum in water is prepared, by introducing:
• This emulsion is introduced at the rate of 27.46 kg / h into the sheath of the twin screw machine which immediately follows the introduction of the alumina powder.
• the passage time of the powder in the machine is of the order of 50 to 60 s.
• a homogeneous paste is obtained which can be extruded.
• Step a 2 - Starting alumina - The same alumina is used as in Example 1.
• Step b 2 Formation of beads -
• the alumina is mixed with wood flour as a porogen (20% by weight relative to the alumina), then shaped in a granulator with a rotating bowl. To allow this shaping, water is added.
• the alumina beads obtained have a diameter between 1, 5 and 4 mm.
• Step c 2 Maturing of the balls -
• Step d 2 Mixing / extrusion -
• the mixing process used is a continuous process in a corrosive twin-screw mixer. Upstream of the mixer, the alumina balls are introduced at a flow rate of 90 kg / h.
• a 2.42% nitric acid solution is introduced at a rate of 10.9 kg / h.
• a 2.1% ammonia solution is introduced at a rate of 4.2 kg / h.
• the passage time of the material in the machine is of the order of 50 s.
• the paste obtained is extruded through a die having orifices with a diameter of 1.6 mm.
• Step e 2 - Drying / calcination - The extrudates are then dried at 140 ° C for 2 h and calcined for 2 h at a calcination temperature indicated in Table 3.
• the extrudates thus calcined have a specific surface which is adjusted between 120 and 200 m 2 / g.
• Stage f 2 - Hydrothermal treatment The extrudates obtained are impregnated with a solution of nitric acid and acetic acid in the following concentrations: 3.5 % nitric acid based on the weight of alumina and 6.5% acetic acid based on the weight of alumina. Then they are subjected to a hydrothermal treatment in a rotary basket autoclave under the conditions defined in Table 3.
• the extrudates are subjected to calcination at a temperature of 550 ° C. for 2 h.
• the characteristics of the extrudates obtained are collated in Table 3.
• the boehmite level is measured on the extrudates before final calcination.
• the extrudates of Example 1 above are dry impregnated with an aqueous solution containing nickel and molybdenum salts.
• the nickel salt is nickel nitrate Ni (NO 3 ) .6H 2 O and the molybdenum salt is ammonium heptamolybdate M ⁇ 7 ⁇ 24 (NH 4 ) 6 .4H 2 O.
• the impregnated extrudates After maturation at room temperature in an atmosphere saturated with water, the impregnated extrudates are dried overnight at 120 ° C., then calcined at 550 ° C. for 2 hours in air.
• the final MoO 3 content is 6.5% by weight, and that of NiO 1, 4% by weight.
• the extrudates of the previous example 5 are impregnated to dryness with an aqueous solution containing nickel and molybdenum salts.
• the nickel salt is nickel nitrate Ni (NO 3 ) 2 .6H O and the molybdenum salt is ammonium heptamolybdate M ⁇ 7 ⁇ 24 (NH 4 ) 6 .4H 2 O.
• the impregnated extrudates After maturation at room temperature in an atmosphere saturated with water, the impregnated extrudates are dried overnight at 120 ° C., then calcined at 550 ° C. for 2 hours in air.
• the final MoO 3 content is 12.5% by weight and that of NiO 3.0% by weight.
• the extrudates of the preceding Example 8 are impregnated to dryness with an aqueous solution containing nickel and molybdenum salts.
• the nickel salt is nickel nitrate Ni (NO 3 ) 2 .6H 2 O and the molybdenum salt is ammonium heptamolybdate Mo 7 O 24 (NH 4 ) 6. 4H 2 O.
• Alumina beads are prepared from the starting alumina of Example 1.
• the alumina is ground with a ball mill to obtain a powder with an average particle diameter of 7 ⁇ m.
• This alumina is mixed with wood flour as a porogen (15% by weight), then shaped in a rotating bezel. To allow this shaping, water is added.
• the beads obtained are dried and calcined. These beads are then subjected to a maturation step by passing steam at 100 ° C for 24 hours.
• the beads are dried for 4 hours at 100 ° C. and calcined for 2 hours at 650 ° C.
• the beads with a particle size between 1, 2 and 2.8 mm are selected.
• the above beads are dry impregnated with an aqueous solution containing nickel and molybdenum salts.
• the nickel salt is nickel nitrate Ni (NO 3 ) 2 .6H 2 O and the molybdenum salt ammonium heptamolybdate Mo 7 O 24 (NH 4 ) 6. 4H 2 O.
• the impregnated extrudates are dried overnight at 120 ° C., then calcined at 550 ° C. for 2 hours in air.
• the final MoO 3 content is 11.0% by weight, and that of NiO 2.6% by weight.
• catalysts D are as follows: - VPT: 0.97 cm 3 / g
• the catalysts obtained are subjected to a hydrotreatment test of various petroleum residues. It is primarily an atmospheric residue (AR) of Middle Eastern origin (Arabian Light) and secondly an atmospheric residue of Venezuelan extra heavy crude (Boscan). These two residues are characterized by high viscosities, high contents of Conradson carbon and asphaltenes. RA Boscan also contains very high nickel and vanadium contents. The characteristics of these residues are summarized in Table 4. Table 4
• the test is carried out in a pilot unit for hydrotreating petroleum residues comprising a tubular reactor in a fixed bed.
• the reactor is filled with one liter of catalyst.
• the flow of fluids (petroleum residue + hydrogen recycling) is ascending in the reactor.
• This type of pilot unit is representative of the operation of one of the reactors of the HYVAHL unit of the French Petroleum Institute for hydroconversion of residues in fixed beds.
• the unit After a sulphurization step by circulation in the reactor of a gas oil fraction supplemented with dimethyldisulfonate (DMDS) at a final temperature of 350 ° C., the unit is operated with the petroleum residues described above under the following operating conditions:
• DMDS dimethyldisulfonate
• the hydrodesulfurization rate is defined as follows:
• HDS (% by weight) 100 X [(% by weight S) load - (% by weight S) recipe J / (% by weight S) load
• the load is then changed by passing the RA Boscan.
• the conduct of the test aims to maintain a constant HDM rate around 80% by weight throughout the cycle. For this, the deactivation of the catalyst is compensated for by a gradual increase in the reaction temperature.
• the test is stopped when the reaction temperature reaches 420 ° C., a temperature considered to be representative of the end-of-cycle temperature of an industrial residue hydroconversion unit.
• the catalysts in the form of extrudates of the present invention can lead to higher HDS performance than that of the comparative catalyst D while ensuring identical performance both in HDM and in retention of nickel + vanadium metals. Superior HDS performance is observed on both a light Arabic and Boscan atmospheric residue.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Geology (AREA)
• Analytical Chemistry (AREA)
• Catalysts (AREA)
• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=9507787

Family Applications (1)

Country Status (7)

Cited By (5)

Families Citing this family (9)

Citations (10)

Family Cites Families (4)

• 1997
  • 1997-06-10 FR FR9707146A patent/FR2764208B1/fr not_active Expired - Fee Related
• 1998
  • 1998-06-10 US US09/445,753 patent/US6656875B1/en not_active Expired - Lifetime
  • 1998-06-10 AU AU79254/98A patent/AU7925498A/en not_active Abandoned
  • 1998-06-10 EP EP98929535A patent/EP0991466B1/fr not_active Expired - Lifetime
  • 1998-06-10 JP JP50177499A patent/JP4264852B2/ja not_active Expired - Fee Related
  • 1998-06-10 WO PCT/FR1998/001186 patent/WO1998056499A1/fr not_active Ceased
  • 1998-06-10 DE DE69827255T patent/DE69827255T2/de not_active Expired - Lifetime

Patent Citations (10)

Also Published As

Similar Documents

Legal Events