MESOPOROUS AND MACROPOROUS COMALAXATED NICKEL ACTIVE PHASE CATALYST HAVING MEDIAN MACROPOROUS DIAMET

专利摘要:
The invention relates to a catalyst comprising a predominantly calcined aluminum oxide matrix and an active phase comprising nickel, said active phase being at least partially comalaxed within said calcined aluminum oxide matrix, the nickel content being between 5 and 65 % weight of said element relative to the total mass of the catalyst, said active phase not comprising any Group VIB metal, the nickel particles having a diameter of less than 15 nm, said catalyst having a mesoporous median diameter of between 12 nm and 25 nm. nm, a median macroporous diameter between 50 and 300 nm, a mesoporous volume measured by mercury porosimetry greater than or equal to 0.40 ml / g and a total pore volume measured by mercury porosimetry greater than or equal to 0.45 ml / g. The invention also relates to the process for preparing said catalyst and its use in a hydrogenation process.
公开号:FR3022160A1
申请号:FR1455429
申请日:2014-06-13
公开日:2015-12-18
发明作者:Malika Boualleg；Anne-Claire Dubreuil；Emily Maille；Cecile Thomazeau
申请人:IFP Energies Nouvelles IFPEN；
IPC主号:

专利说明:

[0001] FIELD OF THE INVENTION The subject of the invention is a comalaxially active nickel phase catalyst having a texture and a formulation which are favorable to hydrogenation reactions, in particular to the reactions of selective hydrogenation of polyunsaturated compounds or of hydrogenation of aromatics. The invention also relates to the process for preparing said catalyst as well as its use in hydrogenation reactions. The most active catalysts in hydrogenation reactions are conventionally based on noble metals such as palladium or platinum. These catalysts are used industrially in refining and in petrochemistry for the purification of certain petroleum fractions by hydrogenation, in particular in reactions of selective hydrogenation of polyunsaturated molecules such as diolefins, acetylenics or alkenylaromates, or in hydrogenation reactions. aromatics. It is often proposed to substitute palladium for nickel, a less active metal than palladium, which is therefore necessary to have a larger quantity in the catalyst. Thus, nickel-based catalysts generally have a metal content of between 5 and 60 wt.% Nickel relative to the catalyst. The speed of the hydrogenation reaction is governed by several criteria, such as the diffusion of the reagents on the surface of the catalyst (external diffusional limitations), the diffusion of the reagents in the porosity of the support towards the active sites (internal diffusion limitations). and the intrinsic properties of the active phase such as the size of the metal particles and the distribution of the active phase within the support. With regard to the internal diffusion limitations, it is important that the porous distribution of the macropores and mesopores is adapted to the desired reaction in order to ensure the diffusion of the reagents in the porosity of the support towards the active sites as well as the diffusion of the formed products. outwards. The importance of a suitable porous distribution and in particular the presence of macropores in a selective hydrogenation reaction of a pyrolysis gasoline in the case of a palladium-based catalyst has for example been described by Z.Zhou, T. Zeng, Z. Cheng, W. Yuan, in AICHE Journal, 2011, Vol. 57, No. 8, pages 2198-2206. As regards the size of the metal particles, it is generally accepted that the catalyst is all the more active as the size of the metal particles is small. In addition, it is important to obtain a particle size distribution centered on the optimum value and a narrow distribution around this value. The often important content of nickel in the hydrogenation catalysts requires particular synthetic routes.
[0002] The most conventional way of preparing these catalysts is the impregnation of the support with an aqueous solution of a nickel precursor, followed generally by drying and calcination. Before their use in hydrogenation reactions these catalysts are generally reduced in order to obtain the active phase which is in metallic form (that is to say in the state of zero valence). The nickel-based catalysts on alumina prepared by a single impregnation step generally make it possible to attain nickel contents of between 12 and 15% by weight of nickel, depending on the pore volume of the alumina used. When it is desired to prepare catalysts having a higher nickel content, several successive impregnations are often necessary to obtain the desired nickel content, followed by at least one drying step, then possibly a calcination step between each impregnation. . Thus, the document WO2011 / 080515 describes a catalyst based on nickel on hydrogenation-active alumina, in particular aromatics, said catalyst having a nickel content greater than 35% by weight, and a large dispersion of the nickel metal on the surface of an alumina. with very open porosity and high surface area. The catalyst is prepared by at least four successive impregnations. The preparation of nickel catalysts having a high nickel content by the impregnation route thus involves a sequence of numerous steps which increases the associated manufacturing costs.
[0003] Another route of preparation also used to obtain catalysts with a high nickel content is coprecipitation. The coprecipitation generally consists of a simultaneous casting in a batch reactor of both an aluminum salt (aluminum nitrate for example) and a nickel salt (nickel nitrate for example). Both salts precipitate simultaneously. Then calcination at high temperature is necessary to make the transition from alumina gel (boehmite for example) to alumina. By this preparation route, contents up to 70% by weight of nickel are reached. Catalysts prepared by coprecipitation are described, for example, in US 4,273,680, US Pat. No. 5,518,851 and US 2010/0116717. Finally, we also know the preparation route by comalaxing. Comalaxing generally consists of a mixture of a nickel salt with an alumina gel such as boehmite, said mixture being subsequently shaped, generally by extrusion, then dried and calcined. US 5,478,791 discloses a nickel-on-alumina catalyst having a nickel content of between 10 and 60 wt.% And a nickel particle size of 15 to 60 nm prepared by the comalaxing of a nickel compound. with an alumina gel, followed by shaping, drying and reduction. In this context, one of the objectives of the present invention is to provide a co-axial nickel active phase catalyst with hydrogenation performance in terms of activity at least as good as the catalysts known from the state of the art. More particularly, the invention relates to a catalyst comprising a calcined predominantly aluminum oxide matrix and an active phase comprising nickel, said active phase being at least partly comalaxed within said oxide matrix, which is predominantly aluminized, the nickel content being between 5 and 65% by weight of said element relative to the total mass of the catalyst, said active phase not comprising a group VIB metal, the nickel particles having a diameter of less than 15 nm, said catalyst having a median mesoporous diameter of between 12 nm and 25 nm, a median macroporous diameter between 50 and 300 nm, a mesoporous volume measured by mercury porosimetry greater than or equal to 0.40 ml / g and a total pore volume measured by mercury porosimetry greater than or equal to 0, 45 mL / g.
[0004] The Applicant has discovered that the comalaxing of a predominantly calcined aluminum oxide matrix derived from a particular alumina gel prepared according to the method of preparation described below with an active phase comprising nickel, makes it possible to obtain a catalyst. which has a porous distribution and a size of nickel particles particularly suitable for hydrogenation reactions, in particular reactions for selective hydrogenation of polyunsaturated molecules such as diolefins, acetylenics or alkenylaromatiques, or hydrogenation reactions of aromatics. The resulting porous distribution of the method of preparation by comalaxing a calcined aluminum oxide matrix obtained from a specific alumina gel, and in particular the presence of macropores, makes it possible to provide a porosity that is particularly suitable for promoting the diffusion of the reagents into the porous medium and then their reaction with the active phase. In fact, in addition to the reduction in the number of stages and therefore in the manufacturing cost, the advantage of a comalaxing compared to an impregnation is that it avoids any risk of reducing the pore volume, or even partial blockage of the porosity of the support during the deposition of the active phase and thus the appearance of internal diffusion limitations. The catalyst according to the invention has the particularity of being able to contain high amounts of active phase. Indeed, the fact of preparing the catalyst according to the invention by comalaxing makes it possible to strongly charge this catalyst in the active phase in a single pass. It is important to emphasize that the catalyst according to the invention differs structurally from a catalyst obtained by simple impregnation of a metal precursor on the alumina support in which the alumina forms the support and the active phase is introduced into the pores of this support. Without being bound by any theory, it appears that the process for preparing the catalyst according to the invention by comalaxing a particular aluminous porous oxide with one or more nickel precursors of the active phase makes it possible to obtain a composite in which the nickel particles and alumina are intimately mixed thereby forming the catalyst structure with a porosity and an active phase content suitable for the desired reactions.
[0005] According to one variant, the catalyst has a macroporous volume of between 10 and 40% of the total pore volume. According to one variant, the catalyst does not have micropores. According to one variant, the nickel content is between 10 and 34% by weight of said element relative to the total mass of the catalyst. According to one variant, the nickel particles have a diameter of between 1.5 and 12 nm. According to one variant, the active phase is entirely comalaxed. According to another variant, part of the active phase is impregnated on the predominantly aluminized calcined oxide matrix. The invention also relates to the process for preparing said catalyst. The invention also relates to the use of the catalyst in a hydrogenation process in which the catalyst according to the invention or capable of being prepared according to the preparation process according to the invention is brought into contact in the presence of hydrogen with a hydrocarbon feed containing polyunsaturated and / or aromatic molecules so as to obtain an effluent that is at least partially hydrogenated. DETAILED DESCRIPTION The Catalyst According to the Invention The catalyst according to the invention is in the form of a composite comprising a calcined predominantly aluminum oxide matrix within which the active phase comprising nickel is distributed. The characteristics of the alumina gel having led to obtaining the alumina mainly contained in said oxide matrix, as well as the textural properties obtained with the active phase, confer on the catalyst according to the invention its specific properties. More particularly, the invention relates to a catalyst comprising a calcined predominantly aluminum oxide matrix and an active phase comprising nickel, said active phase being at least partly comalaxed within said oxide matrix, which is predominantly aluminized, the nickel content being between 5 and 65% by weight of said element relative to the total mass of the catalyst, said active phase not comprising a group VIB metal, the nickel particles having a diameter of less than 15 nm, said catalyst having a median mesoporous diameter of between 12 nm and 25 nm, a median macroporous diameter between 50 and 300 nm, a mesoporous volume measured by mercury porosimetry greater than or equal to 0.40 ml / g and a total pore volume measured by mercury porosimetry greater than or equal to 0, 45 mL / g. The nickel content is between 5 and 65% by weight of said element relative to the total mass of the catalyst, preferably between 8 and 55% by weight, more preferably between 10 and 40% by weight, and particularly preferably preferred between 10 and 34% by weight. The Ni content is measured by X-ray fluorescence. When it is desired to use the catalyst according to the invention in a selective hydrogenation reaction of polyunsaturated molecules such as diolefins, acetylenes or alkenyl aromatics, the nickel content is advantageously included. between 5 and 25% by weight, preferably between 8 and 25% by weight, and more preferably between 10 and 23% by weight of said element relative to the total mass of the catalyst. When it is desired to use the catalyst according to the invention in a reaction for the hydrogenation of aromatics, the nickel content is advantageously between 15 and 65% by weight, preferably between 18 and 55% by weight, and more preferably between between 19 and 34% by weight of said element relative to the total mass of the catalyst. The size of the nickel particles in the catalyst according to the invention is less than 15 nm, preferably between 1.5 and 12 nm, and preferably between 2 and 10 nm. The term "size of the nickel particles" is understood to mean the diameter of the crystallites of nickel in oxide form. The diameter of nickel crystallites in oxide form is determined by X-ray diffraction from the width of the diffraction line at the angle 2theta = 43 ° (i.e. in the crystallographic direction [200] ]) using Scherrer's relationship. This method, used in X-ray diffraction on powders or polycrystalline samples which connects the half-height width of the diffraction peaks to the particle size, is described in detail in the reference: Appl. Cryst. (1978), 11, 102-113 "Scherrer after sixty years: A survey and some new results in the determination of crystallite size", J. I. Langford and A. J. C. Wilson.
[0006] The active phase of the catalyst may further comprise at least one additional metal selected from Group VIII metals, Group IB metals and / or tin. Preferably, the additional metal of group VIII is chosen from platinum, ruthenium and rhodium, as well as palladium. Advantageously, the additional metal of group IB is chosen from copper, gold and silver. The additional metal (s) of the group VIII and / or of the group IB is (are) preferably present at a content representing from 0.01 to 20% by weight of the mass of the catalyst, preferably from 0.05 to 10% by weight of the catalyst mass and even more preferably from 0.05 to 5% by weight of the mass of said catalyst. The tin is preferably present at a content representing from 0.02 to 15% by weight of the catalyst mass, such that the Sn / Ni molar ratio is between 0.01 and 0.2, preferably between 0.025 and 0.055, and even more preferably between 0.03 to 0.05. The active phase of the catalyst does not include a Group VIB metal. It does not include molybdenum or tungsten.
[0007] Without wishing to be bound by any theory, it seems that the particular textural properties of the catalyst according to the invention, in particular a bimodal porosity with a high mesoporous volume coupled with a large macroporous volume and a small size of nickel particles make it possible to obtain a catalyst having hydrogenation performance in terms of activity at least as good as the catalysts known from the state of the art. The catalyst according to the invention also comprises a predominantly calcined aluminum oxide matrix. Said matrix has a calcined alumina content greater than or equal to 90% by weight relative to the total weight of said matrix, optionally supplemented with silica and / or phosphorus at a total content of at most 10% by weight in SiO 2 equivalent and or P205, preferably less than 5% by weight, and very preferably less than 2% by weight relative to the total weight of said matrix. Silica and / or phosphorus can be introduced by any technique known to those skilled in the art, during the synthesis of the alumina gel or during the comalaxing. Even more preferably, the predominantly calcined aluminum oxide matrix consists of alumina. Preferably, the alumina present in said matrix is a transition alumina such as gamma, delta, theta, chi, rho or eta alumina, alone or as a mixture. More preferably, the alumina is a gamma, delta or theta transition alumina, alone or as a mixture. Said catalyst with active phase comalaxée according to the invention is generally presented in all the forms known to those skilled in the art, for example in the form of beads (generally having a diameter of between 1 and 6 mm), extruded tablets , hollow cylinders. Preferably, it consists of extrudates of diameter generally between 0.5 and 10 mm, preferably between 0.8 and 3.2 mm and very preferably between 1.0 and 2.5 mm. This may advantageously be in the form of cylindrical, multilobed, trilobed or quadrilobed extrudates. Preferably its shape will be trilobed or quadrilobed. The shape of the lobes can be adjusted according to all known methods of the prior art. The comalaxed catalyst according to the invention has particular textural properties, in particular a specific porous distribution, where the macroporous and mesoporous volumes are measured by mercury intrusion and the microporous volume is measured by nitrogen adsorption.
[0008] "Macropores" means pores whose opening is greater than 50 nm. By "mesopores" is meant pores whose opening is between 2 nm and 50 nm, limits included. By "micropores" is meant pores whose opening is less than 2 nm. The term "total pore volume of the catalyst" means the volume measured by mercury porosimeter intrusion according to ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm. and an angle of contact of 1400. The angle of wetting was taken equal to 140 ° according to the recommendations of the book "Techniques of the engineer, treated analysis and characterization", pages 1050-1055, written by Jean Charpin and Bernard Rasneur.
[0009] In order to obtain a better accuracy, the value of the total pore volume corresponds to the value of the total pore volume measured by mercury porosimeter intrusion measured on the sample minus the value of the total pore volume measured by mercury porosimeter intrusion measured on the same sample for a pressure corresponding to 30 psi (about 0.2 MPa).
[0010] The volume of macropores and mesopores is measured by mercury intrusion porosimetry according to ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle of 140 °. The value at which mercury fills all the intergranular voids is fixed at 0.2 MPa, and it is considered that beyond this mercury enters the pores of the sample. The macroporous volume of the catalyst is defined as the cumulative volume of mercury introduced at a pressure of between 0.2 MPa and 30 MPa, corresponding to the volume contained in the pores with an apparent diameter greater than 50 nm. The mesoporous volume of the catalyst is defined as the accumulated volume of mercury introduced at a pressure of between 30 MPa and 400 MPa, corresponding to the volume contained in the pores with an apparent diameter of between 2 and 50 nm. The micropore volume is measured by nitrogen porosimetry. The quantitative analysis of the microporosity is carried out using the "t" method (Lippens-De Boer method, 1965) which corresponds to a transformation of the starting adsorption isotherm as described in the book "Adsorption". by powders and porous solids. Principles, methodology and applications "written by F. Rouquerol, J. Rouquerol and K. Sing, Academic Press, 1999. The median mesoporous diameter is also defined as the diameter such that all the pores, among all the pores constituting the mesoporous volume, smaller than this diameter constitute 50% of the total mesoporous volume determined by mercury porosimeter intrusion. The macroporous median diameter is also defined as the diameter such that all the pores, among all the pores constituting the macroporous volume, of size less than this diameter constitute 50% of the total macroporous volume determined by intrusion into the mercury porosimeter. By the specific surface of the catalyst is meant the specific surface B.E.T. determined by nitrogen adsorption according to ASTM D 3663-78 established from the BRUNAUER-EMMETT-TELLER method described in the journal "The Journal of the American Society", 60, 309, (1938). In the following, groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, publisher CRC Press, editor in chief D.R. Lide, 81st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification. The catalyst according to the invention has a total pore volume of at least 0.45 ml / g, preferably at least 0.48 ml / g, and particularly preferably between 0.50 and 0.90 ml. / g. The catalyst according to the invention advantageously has a macroporous volume of between 10 and 40% of the total pore volume, preferably between 10 and 35% of the total pore volume, and even more preferably between 15 and 30% of the pore volume. total. The mesoporous volume of the catalyst is at least 0.40 ml / g, preferably at least 0.45 ml / g, and particularly preferably between 0.45 ml / g and 0.65 ml / g. . The median mesoporous diameter is between 12 nm and 25 nm, and preferably between 12 and 22 nm, and particularly preferably between 13 and 20 nm.
[0011] The catalyst has a macroporous median diameter of between 50 and 300 nm, preferably between 80 and 250 nm, even more preferably between 90 and 200 nm. The catalyst according to the present invention has a specific surface B.E.T. at least 40 m 2 / g, preferably at least 50 m 2 / g, and even more preferably between 55 and 250 m 2 / g. Preferably, the catalyst has a low microporosity, very preferably it has no microporosity. The present invention also relates to a process for preparing said catalyst according to the invention. The catalyst according to the invention with a comalaxed active phase is prepared from a specific alumina gel. The particular porous distribution observed in the catalyst is in particular due to the process of preparation from the specific alumina gel.
[0012] The process for preparing the alumina gel comprises a first precipitation step, a heating step, a second precipitation step and a filtration step. The gel is then subjected to a drying step to obtain a powder. The powder is then subjected to a heat treatment to obtain a calcined aluminous porous oxide. The calcined aluminous porous oxide is then kneaded with a solution comprising the salt (s) of the precursor (s) of the active phase in order to obtain a paste. This paste is then shaped and dried to obtain a dried catalyst. Then the dried catalyst is optionally subjected to heat treatment, then generally reduced and subjected to a passivation treatment.
[0013] More particularly, the process for preparing the catalyst according to the invention comprises the following steps: a) a first step of precipitation, in an aqueous reaction medium, of at least one basic precursor chosen from sodium aluminate, sodium aluminate, potassium, ammonia, sodium hydroxide and potassium hydroxide and at least one acid precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid, in which at least one of the basic or acidic precursors comprises aluminum, the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of between 8.5.degree. and 10.5 and the flow rate of the aluminum-containing acidic and basic precursor (s) is adjusted so as to obtain a forwarding rate of the first step of between 5 and 13%, the rate of progress being defined as being the proport alumina ion formed in equivalent A1203 during said first precipitation step relative to the total amount of alumina formed in equivalent A1203 at the end of step c) of the preparation process, said step operating at a temperature of between 20 and 90 ° C and for a period of between 2 and 30 minutes, b) a heating step of the suspension obtained in step a) at a temperature between 40 and 90 ° C for a period of time between 7 and 45 minutes to obtain an alumina gel, c) a second step of precipitation of the suspension obtained at the end of the heating step b) by adding to the suspension of at least one basic precursor chosen from aluminate sodium hydroxide, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, nitrate aluminum, sulfuric acid, hydrochloric acid and nitric acid, wherein at least one of the basic or acidic precursors comprises aluminum, the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10.5 and the flow rate of the aluminum-containing acidic and basic precursor (s) is adjusted to obtain a second step progress rate of between 87 and 95%, the feed rate being defined as the proportion of alumina formed in equivalent A1203 during said second precipitation step relative to the total amount of alumina formed in Al 2 O 3 equivalent at the end of step c) of the preparation process, said step operating at a temperature of between 40 and 90 ° C and for a period of between 2 and 50 minutes, d) a filtration step of the suspension obtained at the end of step c) of second precipitation to obtain an alumina gel, e) a step of drying of said alumina gel obtained in step d) to obtain a powder, f) a step of heat treatment of the powder obtained at the end of step e) at a temperature of between 500 and 1000 ° C., presence or absence of a flow of air containing up to 60% by volume of water to obtain a calcined aluminous porous oxide, g) a step of mixing the calcined aluminous porous oxide obtained in step f) with a solution comprising at least one nickel precursor to obtain a paste, h) a step of forming the paste obtained, i) a step of drying the shaped dough at a temperature of between 15 and less than 250 ° C, so as to obtain a dried catalyst, j) optionally a heat treatment of said dried catalyst at a temperature between 250 and 1000 ° C in the presence or absence of water. Step a) First precipitation This step consists in bringing into contact, in an aqueous reaction medium, at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid, and nitric acid, in wherein at least one of the basic or acidic precursors comprises aluminum, the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10.5 and the flow rate of the aluminum-containing acidic and basic precursors are set so as to obtain a degree of progress of the first step of between 5 and 13%, the degree of progress being defined as the proportion of alumina formed in equivalent A1203 during said first step of precipitation with respect to the total amount of alumina formed in A1203 equivalent at the end of step c) of the preparation process, said step operating at a temperature of between 20 and 90 ° C., and for a period of time between 2 and 30 minutes. The mixture in the aqueous reaction medium of at least one basic precursor and at least one acidic precursor requires that at least one of the acidic or basic precursors comprises aluminum. It is also possible that at least two of the basic and acidic precursors comprise aluminum. Basic precursors comprising aluminum are sodium aluminate and potassium aluminate. The preferred basic precursor is sodium aluminate. Acidic precursors comprising aluminum are aluminum sulphate, aluminum chloride and aluminum nitrate. The preferred acidic precursor is aluminum sulphate. According to the invention, the alumina acid precursors and the basic alumina precursors can be used alone or as a mixture in the precipitation step.
[0014] Preferably, the basic precursor (s) and acid (s) are added in said first precipitation step a) in aqueous solution. Preferably, the aqueous reaction medium is water. Preferably, said step a) operates with stirring. Preferably, said step a) is carried out in the absence of organic additive. According to the invention, the relative flow rate of the acidic and basic precursors they contain from aluminum or not, is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10.5, preferably between 8.5 and 10, and very preferably between 8.7 and 9.9. In the preferred case where the basic and acidic precursors are respectively sodium aluminate and aluminum sulphate, the mass ratio of said basic precursor to said acidic precursor is advantageously between 1.60 and 2.05. For the other basic and acidic precursors, whether they contain aluminum or not, the base / acid mass ratios are established by a curve of neutralization of the base by the acid. Such a curve is easily obtained by the skilled person.
[0015] The first step a) of precipitation is carried out at a temperature between 20 and 90 ° C, preferably between 20 and 70 ° C, and more preferably between 30 and 50 ° C. The first step a) of precipitation is carried out for a duration of between 2 and 30 minutes, preferably between 5 and 20 minutes, and particularly preferably between 5 to 15 minutes. According to the invention, the rate of progress of said first precipitation step a) is between 5 and 13%, preferably between 6 and 12%, and preferably between 7 and 11%. The rate of progress for each of the precipitation steps is defined as the proportion of alumina formed in Al 2 O 3 equivalent during said first or second precipitation relative to the total amount of alumina formed in Al 2 O 3 equivalent at the end of two precipitation steps and more generally after the steps of preparation of the alumina gel and in particular at the end of step c) of the preparation process according to the invention.
[0016] The aluminum-containing acidic and basic precursors are thus also introduced in amounts which make it possible to obtain a suspension containing the desired quantity of alumina, as a function of the final concentration of alumina to be reached. Step b) Heating According to the invention, said preparation method comprises a step b) of heating the suspension obtained in step a) at a temperature between 40 and 90 ° C for a period of between 7 and 45 minutes to obtain an alumina gel. Said step of heating the suspension obtained at the end of step a), carried out between said first precipitation step a) and the second precipitation step c) operates at a temperature of between 40 and 90 ° C. preferably between 40 and 80 ° C, preferably between 40 and 70 ° C. Said heating step is carried out for a period of between 7 and 45 minutes, and preferably between 7 and 35 minutes.
[0017] Said heating step is advantageously carried out according to all the heating methods known to those skilled in the art. Step c) Second Precipitation According to the invention, said preparation process comprises a second step of precipitation of the heated suspension obtained at the end of the heating step b), said second stage operating by adding in said suspension a aqueous solution of at least one basic precursor selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from sulfate aluminum, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid, and nitric acid, wherein at least one of the basic precursors or acid comprises aluminum, the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10.5 and the flow rate of the acidic and basic precursor (s) containing aluminum is adjusted so as to obtain a rate of advance the second step of between 87 and 95%, the rate of progress being defined as the proportion of alumina formed in equivalent A1203 during said second precipitation step relative to the total amount of alumina formed in equivalent A1203 at the end of step c) of the preparation process, said step operating at a temperature between 40 and 90 ° C, and for a period of between 2 and 50 minutes. As in the first precipitation step a), the addition to the heated suspension of at least one basic precursor and at least one acidic precursor requires that at least one of the basic or acid precursors comprises aluminum. It is also possible that at least two of the basic and acidic precursors comprise aluminum. Basic precursors comprising aluminum are sodium aluminate and potassium aluminate. The preferred basic precursor is sodium aluminate. Acidic precursors comprising aluminum are aluminum sulphate, aluminum chloride and aluminum nitrate. The preferred acidic precursor is aluminum sulphate.
[0018] Preferably, the basic precursor (s) and acid (s) are added in step c) in aqueous solution. Preferably, the aqueous reaction medium is water. Preferably, said step c) operates with stirring. Preferably, said step C) is carried out in the absence of organic additive.
[0019] As in step a) of precipitation, the relative flow rate of the acidic and basic precursors, whether they contain aluminum or not, is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10. , 5, preferably between 8.5 and 10, even more preferably between 8.7 and 9.9. In the preferred case where the basic and acidic precursors are respectively sodium aluminate and aluminum sulphate, the mass ratio of said basic precursor to said acidic precursor is advantageously between 1.60 and 2.05. For the other basic and acidic precursors, whether they contain aluminum or not, the base / acid mass ratio is established by a curve of neutralization of the base by the acid. Such a curve is easily obtained by the skilled person.
[0020] The second precipitation step is carried out at a temperature between 40 and 90 ° C, preferably between 40 and 80 ° C, preferably between 45 and 70 ° C, and very preferably between 50 and 70 ° C C. The second precipitation step is carried out for a period of between 2 and 50 minutes, preferably between 5 and 45 minutes, and preferably between 7 to 40 minutes. The aluminum precursors are also mixed in amounts to obtain a suspension containing the desired amount of alumina, depending on the final concentration of alumina to be achieved. In particular, said second precipitation step makes it possible to obtain 87 to 95% by weight of alumina with respect to the total amount of alumina formed at the end of the two precipitation stages. As in step a) of precipitation, it is the flow rate of the acidic and basic precursor (s) containing aluminum which is adjusted so as to obtain a progress rate of the second stage between 87 and 95 %, preferably 88 to 94%, most preferably 89 to 93%. The rate of progress for each of the precipitation steps is defined as the proportion of alumina formed in Al 2 O 3 equivalent during said first or second precipitation relative to the total amount of alumina formed in Al 2 O 3 equivalent at the end of two precipitation steps and more generally after the steps of preparation of the alumina gel and in particular at the end of step c) of the preparation process according to the invention. Thus, depending on the concentration of alumina referred to after the two stages a) and c) of precipitation, generally between 20 and 100 g / l, preferably between 20 and 80 g / l, preferably between 20 and 80 g / l, preferably between 20 and 100 g / l, preferably between 20 and 80 g / l, preferably between 20 and 80 g / l. and 50 g / L, the amounts of aluminum to be provided by the acid and / or basic precursors are calculated and the flow rate of the precursors is adjusted according to the concentration of said added aluminum precursors, the amount of water added in the reaction medium and the rate of progress required for each of the precipitation steps.
[0021] As in step a) of precipitation, the flow rates of the acid-containing precursor (s) and / or base (s) containing aluminum depend on the size of the reactor used and thus on the amount of water added to the reaction medium. For example, if one works in a 3 L reactor and that 1L alumina suspension of final Al203 concentration of 50 g / L is targeted, with a targeted advancement rate of 10% for the first precipitation step, 10% of the total alumina must be provided during step a) of precipitation. The precursors of alumina are sodium aluminate at a concentration of 155 g / l in Al 2 O 3 and aluminum sulphate at a concentration of 102 g / l in Al 2 O 3. The precipitation pH of the first step is set at 9.5 and the second at 9. The amount of water added to the reactor is 620 mL. For the first step a) of precipitation operating at 30 ° C and for 8 minutes, the flow rate of aluminum sulfate should be 2.1 mL / min and the sodium aluminate flow rate is 2.6 mL / min. . The mass ratio of sodium aluminate to aluminum sulfate is therefore 1.91.
[0022] For the second precipitation stage, operating at 70 ° C., for 30 minutes, the aluminum sulfate flow rate should be 5.2 mL / min and the sodium aluminate flow rate is 6.3 mL / min. The mass ratio of sodium aluminate to aluminum sulfate is therefore 1.84. Step d) Filtration The process for preparing alumina according to the invention also comprises a step of filtering the suspension obtained at the end of step c) of the second precipitation so as to obtain an alumina gel. Said filtration step is carried out according to the methods known to those skilled in the art.
[0023] Said filtration step is advantageously followed by at least one washing step, preferably with water and preferably from one to three washing steps, with a quantity of water equal to the amount of filtered precipitate. The filterability of the suspension obtained at the end of the two precipitation steps is improved by the low dispersibility of the alumina gel obtained, which makes it possible to improve the productivity of the process according to the invention as well as to allow extrapolation of the process. at the industrial level. Dispersibility is defined as the weight of solid or gel of peptised alumina that can not be dispersed by centrifugation in a 3600 G polypropylene tube for 3 minutes. At the end of step d), an alumina gel, also known as boehmite, having a degree of dispersibility of less than or equal to 15%, preferably of between 5 and 15%, and preferably of between 6 and 15%, is obtained. 14%, and very preferably between 7 and 13%, and even more preferably between 7 and 10% and a boehmite particle size of between 1 and 35 nm and preferably between 2 and 35 nm.
[0024] The low dispersibility rate of the gel thus prepared makes it possible to facilitate the step of shaping said gel according to all the methods known to those skilled in the art and in particular by extrusion kneading, by granulation, by pelletization and by the so-called the drop of oil (dripping).
[0025] Step e) Drying of the Alumina Gel According to the invention, the alumina gel obtained at the end of the second precipitation step c), followed by a filtration step d), is dried in a step e) drying to obtain a powder. Said drying step is generally carried out by drying at a temperature between 20 and 200 ° C and for a period of between 8 and 15 hours, or by atomization or by any other drying technique known to those skilled in the art. In the case where said drying step e) is carried out by atomization, the "cake" obtained at the end of the second precipitation step, followed by a filtration step, is resuspended. Said suspension is then sprayed in fine droplets, in a vertical cylindrical chamber in contact with a stream of hot air to evaporate the water according to the principle well known to those skilled in the art. The powder obtained is driven by the heat flow to a cyclone or a bag filter that will separate the air from the powder.
[0026] Preferably, in the case where said drying step e) is carried out by atomization, the atomization is carried out according to the operating protocol described in the publication Asep Bayu Dani Nandiyanto, Kikuo Okuyama, Advanced Powder Technology, 22, 1-19 , 2011. Step f) Heat treatment of the powder obtained at the end of step e) According to the invention, the powder obtained at the end of step e) of drying is subjected to a step f) heat treatment at a temperature between 500 and 1000 ° C in the presence or absence of a flow of air containing up to 60% by volume of water, to obtain a calcined aluminous porous oxide. Preferably, said heat treatment step f) operates at a temperature of between 540 and 850 ° C. Preferably, said heat treatment step f) operates for a duration of between 2 and 10 hours. The term "heat treatment or hydrothermal" means the temperature treatment respectively without presence or in the presence of water. In the latter case, the contact with the water vapor can take place at atmospheric pressure ("steaming") or autogenous pressure (autoclaving). Several combined cycles of thermal or hydrothermal treatments can be carried out. The temperature of said treatments is between 500 and 1000 ° C, preferably between 540 and 850 ° C.
[0027] In case of hydrothermal treatment, the water content is preferably between 150 and 900 grams per kilogram of dry air, and even more preferably between 250 and 650 grams per kilogram of dry air. Said f) heat treatment step allows the transition of the boehmite to the final alumina. The alumina has a crystallographic structure of the type transition alumina gamma, delta, theta, chi, rho or eta, alone or in mixture. More preferably, the alumina is a gamma, delta or theta transition alumina, alone or as a mixture. The existence of the different crystallographic structures is related to the conditions of implementation of the f) heat treatment step. Step c1) Comalaxaqe In this step, the calcined aluminous porous oxide obtained in step f) is kneaded with a solution comprising at least one nickel precursor to obtain a paste. The active phase is provided by one or more solutions containing at least nickel.
[0028] The said solution (s) may be aqueous or consist of an organic solvent or a mixture of water and at least one organic solvent ( for example ethanol or toluene). Preferably, the solution is aqueous. The pH of this solution may be modified by the possible addition of an acid. According to another preferred variant, the aqueous solution may contain ammonia or ammonium ions NH4. Preferably, said nickel precursor is introduced in aqueous solution, for example in the form of nitrate, carbonate, acetate, chloride, hydroxide, hydroxycarbonate, oxalate, complexes formed by a polyacid or an acid-alcohol and its salts, complexes formed with acetylacetonates, or any other soluble inorganic derivative in aqueous solution, which is brought into contact with said calcined aluminous porous oxide. Preferably, nickel precursor nickel nitrate, nickel chloride, nickel acetate or nickel hydroxycarbonate is advantageously used. Very preferably, the nickel precursor is nickel nitrate or nickel hydroxycarbonate.
[0029] According to another preferred variant, said nickel precursor is introduced into an ammoniacal solution by introducing a nickel salt, for example nickel hydroxide or nickel carbonate, into an ammoniacal solution or into an ammonium carbonate or ammonium carbonate solution. ammonium hydrogen carbonate. The quantities of the nickel precursor (s) introduced into the solution are chosen such that the total nickel content is between 5 and 65% by weight, preferably between 8 and 55% by weight, preferably between 10 and 40% by weight. weight, and particularly preferably between 10 and 34% by weight of said element relative to the total mass of the catalyst. The nickel contents are generally adapted to the intended hydrogenation reaction as described above in the section of the catalyst description. Any other additional element may be introduced into the mixing tank during the comalaxing step or in the solution containing the metal salt or salts of the precursors of the active phase. When it is desired to introduce silica into the matrix, a silicic precursor solution or emulsion may be introduced. When it is desired to introduce phosphorus into the matrix, a solution of phosphoric acid may be introduced. When it is desired to introduce an additional metal chosen from Group VIII metals, Group IB metals and / or tin, a salt chosen from nitrate, sulphate, chloride or any other precursor is advantageously used as precursor. conventional. An additive, for example a chelating agent of organic nature, may advantageously be introduced into the solution if the person skilled in the art deems it necessary.
[0030] Comalaxing is advantageously carried out in a kneader, for example a "Brabender" kneader, well known to those skilled in the art. The calcined alumina powder obtained in step f) and one or more optional additional elements are placed in the tank of the kneader. Then the solution comprising at least one nickel precursor, optionally one or more additional element (s), and optionally deionized water is added to the syringe or with any other means for a period of a few minutes, typically about 2 minutes at a given kneading speed. After obtaining a paste, kneading can be continued for a few minutes, for example about 15 minutes at 50 rpm. The solution comprising at least one nickel precursor can also be added in several times during this comalaxing phase. Step h) Shaping The paste obtained after the comalaxing step g) is then shaped according to any technique known to those skilled in the art, for example extrusion forming methods, by pelletizing, by the method of the drop of oil (dripping) or by granulation at the turntable. Preferably, the dough is extrusion shaped into extrudates of diameter generally between 0.5 and 10 mm, preferably 0.8 to 3.2 mm, and very preferably between 1.0 and 2.5 mm. This may advantageously be in the form of cylindrical, trilobed or quadrilobed extrudates. Preferably its shape will be trilobed or quadrilobed. Very preferably, said comalling step g) and said shaping step h) are combined in a single kneading-extruding step. In this case, the paste obtained after the mixing can be introduced into a piston extruder through a die having the desired diameter, typically between 0.5 and 10 mm. Step i) Drying the shaped dough According to the invention, the shaped dough undergoes drying i) at a temperature of between 15 and below 250 ° C, preferably between 80 and 200 ° C, according to any technique known to those skilled in the art, for a period of typically between 10 minutes and 24 hours. A dried catalyst is obtained. Step i) Heat Treatment of the Dried Catalyst The thus dried catalyst can then undergo a complementary heat treatment or hydrothermal step j) at a temperature of between 250 and 1000 ° C and preferably between 250 and 750 ° C for a period of typically between 15 minutes and 10 hours, with or without water. Several combined cycles of thermal or hydrothermal treatments can be carried out. After this or these treatment (s), the catalyst precursor comprises nickel in oxide form, that is to say in NiO form. In the case where water is added, the contact with the steam can take place at atmospheric pressure ("steaming") or autogenous pressure (autoclaving). In case of hydrothermal treatment, the water content is preferably between 150 and 900 grams per kilogram of dry air, and even more preferably between 250 and 650 grams per kilogram of dry air. In one embodiment, in order to increase the overall active phase content of the catalyst according to the invention, a portion of the metal precursor (s) may be introduced into the catalyst resulting from stage i). or j) or k), according to any method known to those skilled in the art, the most common being that of dry impregnation. One or more additional element (s) may also be introduced, such as an additional metal selected from Group VIII metals, Group IB metals and / or tin, or an additive such as a chelating agent of organic nature by any technique known to those skilled in the art, for example by impregnation. In these cases, said impregnation is advantageously followed by drying and optionally heat treatment. The drying can be carried out at a temperature between 70 and 250 ° C, preferably between 80 and 200 ° C, generally for a period of between 1 and 24 hours. The heat treatment can be carried out at a temperature of between 200 and 1000 ° C., preferably between 250 and 750 ° C., generally for a period of between 15 minutes and 10 hours. It is possible to carry out several impregnations, each impregnation advantageously being followed by drying and possibly heat treatment. In another embodiment, all or the precursor (s) metal (s) is introduced during the preparation by comalaxing the oxide matrix calcined predominantly aluminum and no additional impregnation step will therefore be necessary. The metal precursor (s) of the active phase are fully comalaxed within the predominantly calcined aluminum oxide matrix. Step k) Reduction by a reducing agent Before the use of the catalyst in the catalytic reactor and the implementation of a hydrogenation process, at least one reducing treatment step k) is advantageously carried out in the presence of a reducing gas after steps i) or j) so as to obtain a catalyst comprising nickel at least partially in metallic form. This treatment makes it possible to activate the said catalyst and to form metal particles, in particular nickel in the zero state. Said reducing treatment can be carried out in situ or ex situ, that is to say after or before the catalyst is loaded into the hydrogenation reactor. Said step (k) of reducing treatment can be carried out on the catalyst that has or has not been subjected to the passivation step I), described below. The reducing gas is preferably hydrogen. The hydrogen can be used pure or as a mixture (for example a hydrogen / nitrogen mixture, hydrogen / argon, hydrogen / methane). In the case where hydrogen is used as a mixture, all proportions are possible. Said reducing treatment is carried out at a temperature between 120 and 500 ° C, preferably between 150 and 450 ° C. When the catalyst is not passivated, or undergoes a reducing treatment before passivation, the reducing treatment is carried out at a temperature between 350 and 500 ° C, preferably between 350 and 450 ° C. When the catalyst has been previously passivated, the reducing treatment is generally carried out at a temperature of between 120 and 350 ° C, preferably between 150 and 350 ° C. The duration of the reducing treatment is generally from 2 to 40 hours, preferably from 3 to 30 hours. The rise in temperature to the desired reduction temperature is generally slow, for example set between 0.1 and 10 ° C / min, preferably between 0.3 and 7 ° C / min. The flow rate of hydrogen, expressed in L / hour / g of catalyst, is between 0.1 and 100 L / hour / g of catalyst, preferably between 0.5 and 10 L / hour / g of catalyst, so more preferably between 0.7 and 5 L / hour / gram of catalyst. Step I) Passivation Prior to its implementation in the catalytic reactor, the catalyst according to the invention may optionally undergo a passivation step (step I) with a sulfur or oxygen compound or with CO2 before or after the step of reducing treatment k). This passivation step may be performed ex situ or in situ. The passivation step is performed by the implementation of methods known to those skilled in the art. The sulfur passivation step makes it possible to improve the selectivity of the catalysts and to avoid thermal runaways when starting new catalysts ("run away" in the English terminology). Passivation generally consists in irreversibly poisoning with the sulfur compound the most virulent active sites of the nickel which exist on the new catalyst and thus in attenuating the activity of the catalyst in favor of its selectivity. The passivation step is carried out by the use of methods known to those skilled in the art and, for example, by the use of one of the methods described in patent documents EP0466567, US5153163. , FR2676184, WO2004 / 098774, EP0707890. The sulfur compound is for example selected from the following compounds: thiophene, thiophane, alkylmonosulfides such as dimethylsulfide, diethylsulfide, dipropylsulfide and propylmethylsulfide or an organic disulfide of formula HO-R1-SS-R2-OH such as di-thio- di-ethanol of formula HO-C2H4-SS-C2H4-OH (often called DEODS). The sulfur content is generally between 0.1 and 2% by weight of said element relative to the mass of the catalyst. The passivation step with an oxygenated compound or with CO 2 is generally carried out after a preliminary reducing treatment at elevated temperature, generally between 350 and 500 ° C., and makes it possible to preserve the metallic phase of the catalyst in the presence of air. A second reducing treatment at a lower temperature, generally between 120 and 350 ° C., is then generally carried out. The oxygenated compound is generally air or any other stream containing oxygen. The present invention also relates to the use of the catalyst according to the invention in a hydrogenation process and in particular in a process for the selective hydrogenation of polyunsaturated molecules such as diolefins, acetylenics or alkenylaromatiques, also called styrenics. Monounsaturated organic compounds such as, for example, ethylene and propylene, are at the source of the manufacture of polymers, plastics and other value-added chemicals. These compounds are obtained from natural gas, naphtha or gas oil which have been treated by steam cracking or catalytic cracking processes. These processes are operated at high temperature and produce, in addition to the desired monounsaturated compounds, polyunsaturated organic compounds such as acetylene, propadiene and methylacetylene (or propyne), 1-2-butadiene and 1-3 -butadiene, vinylacetylene and ethylacetylene, and other polyunsaturated compounds whose boiling point corresponds to the C5 + gasoline fraction (gasolines containing hydrocarbon compounds having 5 or more carbon atoms), in particular diolefinic or styrenic compounds or indene. These polyunsaturated compounds are very reactive and lead to spurious reactions in the polymerization units. It is therefore necessary to eliminate them before valuing these cuts.
[0031] Selective hydrogenation is the main treatment developed to specifically remove undesired polyunsaturated compounds from these hydrocarbon feeds. It allows the conversion of the polyunsaturated compounds to the corresponding alkenes or aromatics, avoiding their total saturation and thus the formation of the corresponding alkanes or naphthenes. In the case of steam cracking gasolines used as a filler, the selective hydrogenation also makes it possible to selectively hydrogenate alkenyl aromatics to aromatics by avoiding the hydrogenation of the aromatic rings. The hydrocarbon feedstock treated in the selective hydrogenation process has a final boiling point of less than or equal to 250 ° C and contains at least 2 carbon atoms per molecule and comprises at least one polyunsaturated compound. The term "polyunsaturated compounds" means compounds comprising at least one acetylenic function and / or at least one diene function and / or at least one alkenylaromatic function.
[0032] More particularly, the filler is selected from the group consisting of a C2 steam cracking cut, a steam cracking C3 cut, a steam cracking C4 cut, a steam cracking C5 cut and a steam cracking gasoline also called pyrolysis gasoline. The steam-cracking gasoline or pyrolysis gasoline corresponds to a hydrocarbon fraction whose boiling point is generally between 0 and 250 ° C., preferably between 10 and 220 ° C. The polyunsaturated hydrocarbons to be hydrogenated present in said steam cracking gasoline are, in particular, diolefinic compounds (butadiene, isoprene, cyclopentadiene, etc.), styrenic compounds (styrene, alpha-methylstyrene, etc.) and indene compounds (indene). ). Steam cracking gasoline generally comprises the C5-C12 cut with traces of C3, C4, C13, C14, C15 (for example between 0.1 and 3% by weight for each of these cuts). For example, a charge formed of pyrolysis gasoline generally has the following composition: 5 to 25% by weight of paraffins, 40 to 70% by weight of aromatic compounds, 5 to 20% by weight of mono-olefins, 5 to 40% by weight of diolefins, 1 to 10% by weight of alkenylaromatic compounds and from 20 to 300 ppm by weight of sulfur, all the compounds forming 100%. Preferably, the polyunsaturated hydrocarbon feedstock treated according to the selective hydrogenation process according to the invention is a steam-cracking gasoline. The selective hydrogenation process according to the invention aims at eliminating said polyunsaturated hydrocarbons present in said feedstock to be hydrogenated without hydrogenating the monounsaturated hydrocarbons. For example, when said feed is a C2 cut, the selective hydrogenation process aims to selectively hydrogenate acetylene. When said feedstock is a C3 cut, the selective hydrogenation process aims to selectively hydrogenate propadiene and methylacetylene. In the case of a C4 cut, it is intended to remove butadiene, vinylacetylene (VAC) and butyne, in the case of a C5 cut, it is intended to eliminate pentadienes. When said feed is a steam cracking gasoline, the selective hydrogenation process aims to selectively hydrogenate said polyunsaturated hydrocarbons present in said feed to be treated so that the diolefinic compounds are partially hydrogenated to mono-olefins and that the styrenic and indene compounds are partially hydrogenated to corresponding aromatic compounds by avoiding the hydrogenation of aromatic rings. The technological implementation of the selective hydrogenation process is for example carried out by injection, in ascending or descending current, of the polyunsaturated hydrocarbon feedstock and hydrogen in at least one fixed bed reactor.
[0033] Said reactor may be of the isothermal or adiabatic type. An adiabatic reactor is preferred. The polyunsaturated hydrocarbon feedstock may advantageously be diluted by one or more re-injection (s) of the effluent, from said reactor where the selective hydrogenation reaction occurs, at various points of the reactor, located between the inlet and the outlet. the reactor outlet to limit the temperature gradient in the reactor. The technological implementation of the selective hydrogenation process according to the invention may also be advantageously carried out by implanting at least one of said supported catalyst in a reactive distillation column or in reactor-exchangers. The flow of hydrogen can be introduced at the same time as the feedstock to be hydrogenated and / or at one or more different points of the reactor.
[0034] The selective hydrogenation of the C2, C3, C4, C5 and C5 + cuts can be carried out in the gas phase or in the liquid phase, preferably in the liquid phase for the C3, C4, C5 and C5 + cuts. Indeed, a reaction in the liquid phase makes it possible to lower the energy cost and to increase the cycle time of the catalyst.
[0035] In general, the selective hydrogenation is carried out at a temperature of between 0 and 500 ° C., at a pressure of between 0.1 and 20 MPa, at a molar ratio of hydrogen / (polyunsaturated compounds to be hydrogenated) between 0 and 500 ° C. , 1 and 10 and at an hourly volume velocity VVH (defined as the ratio of the volume flow rate of charge to the volume of the catalyst) between 0.1 and 200 h-1 for a liquid charge, between 100 and 15 000 h-1 for a gaseous charge of a hydrocarbon charge containing polyunsaturated compounds containing at least 2 carbon atoms per molecule and having a final boiling point of less than or equal to 250 ° C. Preferably, a selective hydrogenation process is carried out in which the feedstock is a steam cracking gasoline containing polyunsaturated compounds, the molar ratio (hydrogen) / (polyunsaturated compounds to be hydrogenated) is generally between 1 and 2, the temperature is generally between 40 and 200 ° C, preferably between 50 and 180 ° C, the hourly volume velocity (VVH) is generally between 0.5 and 50 h-1, preferably between 1 and 20 h-1 and the pressure is generally between 0.3 and 6.5 MPa, preferably between 2.0 and 3.5 MPa. The hydrogen flow rate is adjusted in order to dispose of it in sufficient quantity to theoretically hydrogenate all of the polyunsaturated compounds and to maintain an excess of hydrogen at the outlet of the reactor.
[0036] The present invention also relates to the use of the catalyst according to the invention in a hydrogenation process and in particular in a process for the hydrogenation of aromatics making it possible to convert aromatic compounds from petroleum or petrochemical cuts by converting the aromatics. aromatic nuclei to naphthenic rings.
[0037] The hydrocarbon feedstock treated in the aromatic hydrogenation process has a final boiling point less than or equal to 650 ° C, generally between 20 and 650 ° C, and preferably between 20 and 450 ° C, and contains at least less an aromatic or polyaromatic compound. Examples of petroleum or petrochemical cuts containing aromatic compounds include, for example, kerosene, light gas oil, heavy gas oil and cracking distillates, such as FCC recycle oil, coker unit gas oil, distillates and the like. hydrocracking, and the reformate of catalytic reforming. The content of aromatic hydrocarbons in a feed treated in the hydrogenation process is generally between 0.1 and 80% by weight, preferably between 1 and 50% by weight, and particularly preferably between 2 and 35% by weight, the percentage by weight. weight being based on the total weight of the hydrocarbon feed. The aromatics present are, for example, benzene or alkylaromatics such as toluene, ethylbenzene, o-xylene, m-xylene, or p-xylene, or aromatics having a plurality of aromatic (polyaromatic) rings, such as naphthalene. The sulfur or chlorine content of the feedstock is generally less than 5000 ppm by weight of sulfur or chlorine respectively, preferably less than 100 ppm by weight, and particularly preferably less than 10 ppm.
[0038] The technological implementation of the aromatic hydrogenation process can be carried out as described in the selective hydrogenation part. The hydrogenation of the aromatics can be carried out in the gas phase or in the liquid phase, preferably in the liquid phase. In general, the hydrogenation of the aromatics is carried out at a temperature of between 30 and 350 ° C., preferably between 50 and 325 ° C., at a pressure of between 0.1 and 20 MPa, preferably between 0 and 20 ° C. , 5 and 10 MPa, at a molar ratio of hydrogen / (aromatic compounds to be hydrogenated) between 0.1 and 10 and at an hourly volume velocity VVH between 0.05 and 50 h -1, preferably between 0.1 and 10 h -1 of a hydrocarbon feedstock containing aromatic compounds and having a final boiling point of less than or equal to 650 ° C.
[0039] The hydrogen flow rate is adjusted in order to dispose of it in sufficient quantity to theoretically hydrogenate all of the polyunsaturated compounds and to maintain an excess of hydrogen at the outlet of the reactor. The conversion of the aromatic or polyaromatic compounds is generally greater than 20 mol%, preferably greater than 40 mol%, more preferably greater than 80 mol%, and particularly preferably greater than 90 mol% of the aromatic compounds. or polyaromatic content contained in the hydrocarbon feedstock. The conversion is calculated by dividing the difference between the total moles of the aromatic or polyaromatic compounds in the hydrocarbon feedstock and the product by the total moles of the aromatic or polyaromatic compounds in the hydrocarbon feedstock. According to one particular variant, the catalyst according to the invention is used in a process for the hydrogenation of a benzene-containing hydrocarbon feedstock such as, for example, reformate from a catalytic reforming unit. The benzene content is generally between 0.1 and 40% by weight, preferably between 0.5 and 35% by weight, and particularly preferably between 2 and 30% by weight, the percentage by weight being based on the total weight of the hydrocarbon load. The sulfur or chlorine content of the feedstock is generally less than 10 ppm by weight of sulfur or chlorine respectively, and preferably less than 2 ppm by weight.
[0040] The hydrogenation of the feed containing benzene can be carried out in the gas phase or in the liquid phase, preferably in the liquid phase. When carried out in the liquid phase, a solvent may be present. In general, the hydrogenation of benzene is carried out at a temperature of between 30 and 250 ° C., preferably between 50 and 200 ° C., and more preferably between 80 and 180 ° C., at a pressure comprised between between 0.1 and 10 MPa, preferably between 0.5 and 4 MPa, at a hydrogen / (benzene) molar ratio of between 0.1 and 10 and at an hourly volume velocity VVH between 0.05 and 50 h -1, preferably between 0.5 and 10 h -1.
[0041] The conversion of benzene is generally greater than 50 mol%, preferably greater than 80 mol%, more preferably greater than 90 mol% and particularly preferably greater than 98 mol%. The invention is illustrated by the following examples.
[0042] Example 1 Preparation of an aqueous solution of Ni precursors The aqueous solution of Ni precursors (solution S) used for the preparation of catalysts A, B, C and D is prepared by dissolving 46.1 g of nickel nitrate ( NiNO3, supplier Strem Chemicals0) in a volume of 13 mL of distilled water. Solution S is obtained whose NiO concentration is 20.1% by weight (relative to the mass of the solution). EXAMPLE 2 Preparation of the Comalaxed Catalyst A According to the Invention The catalyst A according to the invention is prepared by comalaxing an alumina Al and the solution S of precursors of Ni. The alumina Al synthesis according to the invention is carried out in a six-stage 5 L reactor, named below a) to f). The concentration of the acidic and basic precursors of alumina is as follows: aluminum sulphate Al2 (504) 3 at 102 g / l in Al2O3 and sodium aluminate Naa100 at 155 g / l in Al2O3. It is desired to obtain a final alumina concentration of 45 g / L in the suspension obtained at the end of the second step c) of precipitation. a) A first precipitation of aluminum sulphate Al2 (504) 3 and sodium aluminate NaA100 in 8 minutes at 30 ° C, pH = 9.1 and with a progress rate of 10%. This advancement rate corresponds to the proportion of alumina formed in A1203 equivalent during this first step. b) A rise in temperature of 30 ° C to 70 ° C in 20 to 30 minutes. c) A second precipitation of aluminum sulphate Al2 (504) 3 and sodium aluminate NaA100 in 30 minutes at 70 ° C., pH = 9.1 and with a degree of progress of 90%. This degree of advancement corresponds to the proportion of alumina formed in A1203 equivalent during this second precipitation step. d) Filtration of the suspension obtained at the end of step c) by displacement on a sintered Buchner tool P4, followed by three successive washes with 5 L of distilled water. e) Drying of the alumina gel overnight at 120 ° C. f) A heat treatment by calcination of the powder obtained at the end of step e) at 750 ° C. for 2 hours. Alumina A1 is obtained. Catalyst A is then prepared from alumina Al and solution S of Ni precursors, prepared above, according to the following four steps: g) Co-ordination step: Brabender mixer with a bowl of 80 cm3 and a mixing speed of 30 rpm. Alumina powder Al is placed in the bowl of the kneader. Then solution S of Ni precursors is added to the syringe for about 2 minutes at 15 rpm. After obtaining a paste, the kneading is maintained for 15 minutes at 50 rpm. h) The paste thus obtained is introduced into a piston extruder and is extruded through a 2.1 mm diameter die at 50 mm / min. i) The extrudates thus obtained are then dried overnight in an oven at 80 ° C. A dried catalyst is obtained. j) The dried catalyst is then calcined in a tubular furnace, under a flow of air of 1 L / h / g of catalyst, at 450 ° C for 2 hours (ramp temperature rise of 5 ° C / min). The calcined catalyst A is then obtained. The characteristics of the calcined catalyst A thus obtained are given in Table 1 below. Table 1: Properties of catalysts A (according to the invention), and B, C and D comatives ABCD According to the invention Comparative Comparative Comparative Calcium precursor Calcined Non calcined Calcined Calcined Mode of introduction Comalaxing Comalaxing Dry impregnation Comalaxing Ni Ni (% wt) 19.8 22.9 20.5 19.4 BET surface (m2 / g) 156 232 106 183 Total pore volume (mL / g) 0.73 0.53 0.70 0.84 Mesoporous volume (mL / g) 0.57 0.28 0.54 0.38 Median diameter 16.5 7.3 18.5 7.4 Mesoporous (nm) Macroporous Volume (mL / g) 0.16 0.25 0.16 0.46 Macroporous Volume (° / 0 of total pore volume) 22 47 23 55 Median diameter 185 1057 112.5 1630 macroporous (nm) Microporous volume 0 0.15 0 0 (mL / g) Size of crystallites 7.8 13.3 16.5 11.2 of NiO (nm) Example 3: Preparation of comalaxed catalyst B, from boehmite 5 (comparative) Catalyst B is prepared by comalaxing boehmite (non-calcined alumina gel) and solution S of Ni precursors. The synthesis of the boehmite is carried out in a 5 L reactor by following the first five steps, steps a) to e), of Example 2 described above. The operating conditions are strictly identical. At the end of step e), a boehmite powder B1 is obtained. This boehmite powder B1 is then mixed with the solution S of Ni precursors (described in Example 1). No calcination occurs between step e) and the step of comalaxing.
[0043] Catalyst B is then prepared according to the four steps g) to j) described in Example 2. The operating conditions are strictly identical, with the exception of the following two points: in step g) of comalaxing, the powder boehmite B1 is mixed with solution S of Ni precursors. In the heat treatment stage j), the calcination is carried out at 750 ° C. in order to transform the boehmite into alumina. This calcination at high temperature gave rise to refractory phases of nickel aluminate type. The characteristics of the calcined catalyst B thus obtained are reported in Table 1. Compared to the catalyst A, the macroporous volume is much higher, the mesoporous volume and the mesoporous median diameter are much smaller. Catalyst B also has microporosity, unlike catalyst A. It has NiO crystallites much larger in size than those of catalyst A.
[0044] EXAMPLE 4 Preparation of Catalyst C by Dry Impregnation of an Aluminum Support (Comparative) Catalyst C is prepared by dry impregnation of alumina A1 described in Example 2 with solution S of Ni precursors.
[0045] The alumina Al synthesis is carried out by following the six steps, steps a) to f), of Example 2 described above. The operating conditions are strictly identical. However, a step of shaping the dried alumina gel from step e) is inserted between steps e) and f): The shaping of this powder is carried out on a "Brabender" type kneader with a acid level of 1% (total acid level, expressed relative to dry alumina), a neutralization rate of 20% and acid and basic fire losses of 62% and 64 ° A respectively, then the extrusion is carried out on a piston extruder through a 2.1 mm diameter die. After extrusion, the extrudates are dried overnight at 80 ° C. At the end of the heat treatment step f), extrudates of the alumina Ai are obtained.
[0046] Alumina Al is then impregnated with solution S of precursors of Ni, described in Example 1, according to the so-called dry impregnation method; a volume of 11.5 ml of solution S is added dropwise to a mass of 10.5 g of alumina Al for a period of 10 minutes. After impregnation, the solid is dried in an oven at 120 ° C. overnight, and then calcined under an air flow of 1 L / hr / g of catalyst, at 450 ° C. for 2 hours (ramp for raising the temperature 5 ° C / min). The calcined catalyst C is thus obtained. The characteristics of the calcined catalyst C thus obtained are given in Table 1. It has NiO crystallites of a much larger size than those of the catalyst A. EXAMPLE 5 Preparation of the Comalaxed Catalyst D, from alumina (comparative) Catalyst D is prepared by comalaxing alumina D1 and solution S of precursors of Ni. The synthesis of alumina D1 is carried out by following the six steps, steps a) to f), of Example 2 described above. The operating conditions are strictly identical, with the exception of the following two points: in step a) of first precipitation, the degree of advance is 20 ° A: In the second precipitation step c), the degree of progress is 80 ° A :, At the end of step f), the alumina D1 is obtained in powder form. The catalyst D is then prepared by comalaxing the alumina D1 and the solution S of precursors of Ni described in Example 1 according to the four steps g) to j) described in Example 2. The operating conditions are strictly identical . At the end of step j), the calcined catalyst D is then obtained. The characteristics of the calcined catalyst D thus obtained are reported in Table 1. This catalyst has a macroporous volume which is much higher than that of the catalyst A as well as a mesoporous volume and mesoporous median diameter much lower than those of catalyst A. It also has NiO crystallites larger in size than those of catalyst A. Example 6: Evaluation of the catalytic properties of catalysts A, B, C and D in selective hydrogenation of a mixture containing styrene and isoprene The catalysts A, B, C and D described in the examples above are tested with respect to the reaction of selective hydrogenation of a mixture containing styrene and isoprene. The composition of the filler to be selectively hydrogenated is as follows: 8% by weight styrene (supplier Sigma Aldrich®, purity 99%), 8% by weight isoprene (supplier Sigma Aldrich®, purity 99%), 84% by weight n-heptane (solvent ) (VWRO supplier, purity> 99% chromanorm HPLC). This feed also contains very low sulfur compounds: 10 ppm wt of sulfur introduced in the form of pentanethiol (supplier Fluka0, purity> 97%) and 100 ppm wt of sulfur introduced in the form of thiophene (Merck® supplier, purity 99% ). This composition corresponds to the initial composition of the reaction mixture. This mixture of model molecules is representative of a pyrolysis species. The selective hydrogenation reaction is carried out in a 500 ml autoclave made of stainless steel, equipped with magnetic stirring mechanical stirring and capable of operating at a maximum pressure of 100 bar and temperatures between 5 ° C and 200 ° C. . Prior to its introduction into the autoclave, a quantity of 3 mL of catalyst is reduced ex situ under a flow of hydrogen of 1 L / h / g of catalyst, at 400 ° C. for 16 hours (temperature rise ramp of 1 ° C / min), then it is transferred to the autoclave, protected from the air. After addition of 214 ml of n-heptane (supplier VWRO, purity> 99% chromanorm HPLC), the autoclave is closed, purged, then pressurized under 35 bar (3.5 MPa) of hydrogen, and brought to the temperature of test equal to 30 ° C. At time t = 0, about 30 g of a mixture containing styrene, isoprene, n-heptane, pentanethiol and thiophene are introduced into the autoclave. The reaction mixture then has the composition described above and stirring is started at 1600 rpm. The pressure is kept constant at 35 bar (3.5 MPa) in the autoclave using a reservoir bottle located upstream of the reactor. The progress of the reaction is monitored by taking samples of the reaction medium at regular time intervals: the styrene is hydrogenated to ethylbenzene, without hydrogenation of the aromatic ring, and the isoprene is hydrogenated to methyl-butenes. If the reaction is prolonged longer than necessary, the methyl-butenes are in turn hydrogenated to isopentane. Hydrogen consumption is also monitored over time by the pressure decrease in a reservoir bottle located upstream of the reactor. The catalytic activity is expressed in moles of H2 consumed per minute and per gram of Ni. The catalytic activities measured for catalysts A, B, C and D are reported in Table 2 below. They are related to the catalytic activity measured for catalyst A (AHyci).
[0047] Table 2: Comparison of the performances in selective hydrogenation of a mixture containing styrene and isoprene (AHyci) and hydrogenation of toluene (AHyD2). Catalyst Conform Mode State AHYD1 (%) AHYD2 (%) precursor aluminum precursor Ni A precursor Yes Calcined Comalax 100 100 B No Dried Comalaxing 23.6 25.1 C No Calcined Impregnation 44.7 48.2 sec D No Calcined Comalaxing 71.3 68.9 This shows the improved performance of catalyst A prepared according to the invention. The preparation by alumina comalaxation makes it possible to obtain smaller NiO crystallites and thus improved catalytic performance (comparison with catalyst C). In contrast, the preparation by comalaxing boehmite (catalyst B) leads to a significant decrease in catalytic performance due to the presence of large crystallites of NiO and nickel aluminate refractory phases formed during calcination at high temperature. The specificity of the alumina used to prepare the catalyst A according to the invention is illustrated by comparison with the catalyst D: the fact of preparing the catalyst A from an alumina having textural properties according to the invention makes it possible to obtain a catalyst having improved performance over a catalyst prepared by comalaxing with alumina having different textural properties.
[0048] EXAMPLE 7 Evaluation of the Catalytic Properties of Catalysts A, B, C and D in Hydrogenation of Toluene Catalysts A, B, C and D described in the examples above are also tested with respect to the hydrogenation reaction toluene.
[0049] The selective hydrogenation reaction is carried out in the same autoclave as that described in Example 6. Prior to its introduction into the autoclave, a quantity of 2 ml of catalyst is reduced ex situ under a flow of hydrogen of 1 L / h / g of catalyst at 400 ° C for 16 hours (ramp temperature rise of 1 ° C / min), then it is transferred into the autoclave, protected from air. After addition of 216 ml of n-heptane (supplier VWRO, purity> 99% chromanorm HPLC), the autoclave is closed, purged, then pressurized under 35 bar (3.5 MPa) of hydrogen, and brought to the temperature of test equal to 80 ° C. At time t = 0, about 26 g of toluene (supplier SDSO, purity> 99.8%) are introduced into the autoclave (the initial composition of the reaction mixture is then toluene 6% w / n-heptane 94% wt) and the agitation is started at 1600 rpm. The pressure is kept constant at 35 bar (3.5 MPa) in the autoclave using a reservoir bottle located upstream of the reactor. The progress of the reaction is monitored by taking samples of the reaction medium at regular time intervals: toluene is completely hydrogenated to methylcyclohexane. Hydrogen consumption is also monitored over time by the pressure decrease in a reservoir bottle located upstream of the reactor. The catalytic activity is expressed in moles of H2 consumed per minute and per gram of Ni. The catalytic activities measured for catalysts A, B, C and D are reported in Table 2. They are related to the catalytic activity measured for catalyst A (AHyD2). The improved performances of the catalyst A prepared according to the invention are found.

权利要求:
Claims (15)
[0001]
REVENDICATIONS1. Catalyst comprising a calcined predominantly aluminized oxide matrix and an active phase comprising nickel, said active phase being at least partly comalaxed within said calcined aluminum predominantly oxide matrix, the nickel content being between 5 and 65% by weight of said element by relative to the total mass of the catalyst, said active phase not comprising a group VIB metal, the nickel particles having a diameter of less than 15 nm, said catalyst having a mesoporous median diameter of between 12 nm and 25 nm, a median diameter macroporous between 50 and 300 nm, a mesoporous volume measured by mercury porosimetry greater than or equal to 0.40 ml / g and a total pore volume measured by mercury porosimetry greater than or equal to 0.45 ml / g.
[0002]
2. Catalyst according to claim 1, wherein the macroporous volume is between 10 and 40% of the total pore volume.
[0003]
3. Catalyst according to claims 1 or 2, wherein the nickel content is between 10 and 34% by weight of said element relative to the total mass of the catalyst.
[0004]
4. Catalyst according to claims 1 to 3 having no micropores.
[0005]
5. Catalyst according to claims 1 to 4, wherein the nickel particles have a diameter of between 1.5 and 12 nm.
[0006]
Catalyst according to claims 1 to 5, wherein the active phase is fully comalaxed.
[0007]
7. Catalyst according to claims 1 to 5, wherein a portion of the active phase is impregnated on the calcined aluminum oxide matrix.
[0008]
8. Process for the preparation of a catalyst according to claims 1 to 7, comprising the following steps: a) a first step of precipitation, in an aqueous reaction medium, of at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid, in which at least one of the basic or acidic precursors comprises aluminum, the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of between 8 and , 5 and 10.5 and the flow rate of the aluminum-containing acidic and basic precursor (s) is adjusted so as to obtain a degree of progress of the first step of between 5 and 13%, the rate of progress being defined as the proportion of alumina formed in equivalent A1203 during said first precipitation step relative to the total amount of alumina formed in equivalent A1203 at the end of step c) of the preparation process, said step operating at a temperature of between 20 and 90 ° C and for a period of between 2 and 30 minutes, b) a heating step of the suspension obtained in step a) at a temperature between 40 and 90 ° C for a period of between 7 and 45 minutes for obtaining an alumina gel, c) a second precipitation step of the suspension obtained at the end of the heating step b) by adding to the suspension at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid, in which at least one of the basic or acidic precursors comprises aluminum, the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10.5 and the flow rate. of the aluminum-containing acidic and basic precursor (s) is adjusted so as to obtain a second stage progress rate of between 87 and 95%, the degree of progress being defined as the proportion of alumina formed in equivalent A1203 during said second precipitation step relative to the total amount of alumina formed in equivalent A1203 at the end of step c) of the preparation process, said step operating at a temperature of between 40 and 90 ° C. and for a period of between 2 and 50 minutes, d) a filtration step of the suspension obtained at the end of the second precipitation step c) to obtain an alumina gel, e) a step of drying said gelof alumina obtained in step d) to obtain a powder, f) a step of heat treatment of the powder obtained at the end of step e) at a temperature of between 500 and 1000 ° C., in the presence or absence of not a flow of air containing up to 60% by volume of water to obtain a calcined aluminous porous oxide, g) a step of mixing the calcined aluminous porous oxide obtained in step f) with a solution comprising at least one nickel precursor to obtain a paste, h) a step of forming the paste obtained, i) a step of drying the shaped dough at a temperature between 15 and less than 250 ° C, so as to obtain a dried catalyst, j) optionally a thermal treatment of said dried catalyst at a temperature between 250 and 1000 ° C in the presence or absence of water.
[0009]
9. Process according to claim 8, wherein at least one reducing treatment step k) is carried out in the presence of a reducing gas after steps i) or j) so as to obtain a catalyst comprising nickel at least partially in the form of metallic.
[0010]
10. The method of claim 9 wherein, a passivation step I) is carried out with a sulfur or oxygen compound or with CO2 before or after the reducing treatment step k).
[0011]
11. Method according to one of claims 8 to 10, wherein the rate of advance of the first precipitation step a) is between 6 and 12%.
[0012]
12. Process according to one of claims 8 to 11, in which the acidic precursor of steps a) and c) is chosen from aluminum sulphate, aluminum chloride and aluminum nitrate and in which the precursor The basic steps a) and c) are selected from sodium aluminate and potassium aluminate.
[0013]
13. Hydrogenation process wherein the catalyst according to one of claims 1 to 7 or capable of being prepared according to one of claims 8 to 12 is contacted in the presence of hydrogen with a hydrocarbon charge containing polyunsaturated and / or aromatic molecules so as to obtain an effluent that is at least partially hydrogenated.
[0014]
14. Hydrogenation process according to claim 13, wherein a selective hydrogenation is carried out at a temperature of between 0 and 500 ° C., at a pressure of between 0.1 and 20 MPa, at a molar ratio of hydrogen / (polyunsaturated hydrogenate) between 0.1 and 10 and at an hourly space velocity of between 0.1 and 200 h -1 for a liquid feed, between 100 and 15000 h -1 for a gaseous feed of a hydrocarbon feed containing polyunsaturated compounds containing at least 2 carbon atoms per molecule and having a final boiling point of less than or equal to 250 ° C.
[0015]
15. The hydrogenation process according to claim 13, wherein the aromatics are hydrogenated at a temperature of between 30 and 350 ° C., at a pressure of between 0.1 and 20 MPa, at a molar ratio of hydrogen / (aromatic compounds). to be hydrogenated) between 0.1 and 10 and at a hourly space velocity of between 0.05 and 50 h-1 of a hydrocarbon feedstock containing aromatic compounds and having a final boiling point of less than or equal to 650 ° C.

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同族专利:

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公开号 | 公开日

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RU2683777C2|2019-04-02|

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WO2015189193A1|2015-12-17|

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CN107454860A|2017-12-08|

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US10350580B2|2019-07-16|

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FR3022160B1|2021-05-07|

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RU2017100933A3|2018-12-14|

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EP3154676A1|2017-04-19|

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RU2017100933A|2018-07-16|

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US20180154340A1|2018-06-07|

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CN107454860B|2020-08-11|

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优先权:

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申请号 | 申请日 | 专利标题

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FR1455429A|FR3022160B1|2014-06-13|2014-06-13|ACTIVE PHASE CATALYST OF MESOPOREOUS AND MACROPOREOUS COMALAXED NICKEL WITH A MEDIAN MACROPOREOUS DIAMETER BETWEEN 50 AND 300 NM AND ITS USE IN HYDROGENATION|FR1455429A| FR3022160B1|2014-06-13|2014-06-13|ACTIVE PHASE CATALYST OF MESOPOREOUS AND MACROPOREOUS COMALAXED NICKEL WITH A MEDIAN MACROPOREOUS DIAMETER BETWEEN 50 AND 300 NM AND ITS USE IN HYDROGENATION|

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EP15726215.5A| EP3154676A1|2014-06-13|2015-06-09|Mesoporous and macroporous catalyst with an active phase of nickel obtained by comulling and having a macroporous median diameter of between 50 and 300 nm and use of same in hydrocarbon hydrogenation|

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CN201580030601.XA| CN107454860B|2014-06-13|2015-06-09|Mesoporous and macroporous nickel-blended active phase catalysts having median macropore diameters of 50 to 300 nm and their use in hydrogenation|

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US15/317,839| US10350580B2|2014-06-13|2015-06-09|Catalyst with a mesoporous and macroporous co-mixed nickel active phase having a median macropore diameter in the range 50 to 300 NM, and its use in hydrogenation|

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RU2017100933A| RU2683777C2|2014-06-13|2015-06-09|MACRO- AND MESOPOROUS CATALYST WITH UNIFORM DISTRIBUTION OF ACTIVE PHASE OF NICKEL AND MACROPOROUS MEDIAN DIAMETER BETWEEN 50 AND 300 nm AND USE OF SAME IN HYDROCARBON HYDROGENATION|

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PCT/EP2015/062819| WO2015189193A1|2014-06-13|2015-06-09|Mesoporous and macroporous catalyst with an active phase of nickel obtained by comulling and having a macroporous median diameter of between 50 and 300 nm and use of same in hydrocarbon hydrogenation|