MESOPOROUS CATALYST BASED ON NICKEL AND ITS USE IN HYDROGENATION.

专利摘要:
The invention relates to a supported catalyst comprising a calcined, predominantly aluminum oxide support and an active phase comprising nickel, 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 no Group VIB metal, the nickel particles having a diameter of less than or equal to 20 nm, said catalyst having a mesoporous median diameter greater than or equal to 14 nm, a mesoporous volume measured by mercury porosimetry greater than or equal to 0.45 mL / g, a total pore volume measured by mercury porosimetry greater than or equal to 0.45 mL / g, a macroporous volume of less than 5% of the total pore volume, said catalyst being in the form of grains having a mean diameter of between 0 , 5 and 10 mm. The invention also relates to the process for preparing said catalyst and its use in a hydrogenation process.
公开号:FR3025728A1
申请号:FR1458543
申请日:2014-09-11
公开日:2016-03-18
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 invention relates to a catalyst supported on a nickel-phase calcined predominantly aluminic oxide support having a texture and a formulation which are favorable to hydrogenation reactions, in particular to the selective hydrogenation reactions 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 catalysts for selective hydrogenation or hydrogenation of aromatics are generally based on Group VIII metals of the periodic table of elements such as nickel. The metal is in the form of nanometric metal particles deposited on a support which may be a refractory oxide. The metal content of group VIII, the possible presence of a second metallic element, the size of the metal particles and the distribution of the active phase in the support as well as the nature and porous distribution of the support are parameters that are important. on the performance of the catalysts. 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. 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. 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.
[0002] Numerous developments thus relate to optimizing the porous distribution of the catalyst by optimizing the support of the catalyst. WO2011 / 080515 discloses an alumina supported nickel hydrogenation catalyst having a nickel content of greater than 35% by weight, said catalyst having a high dispersion of nickel (0) on the surface of a porous alumina very open and with a high specific surface. The porous distribution of the support is bimodal: at least 30% of the total pore volume is constituted by pores having a diameter of between 5 and 20 nm, and at least 20% of the total pore volume consists of pores with a diameter of between 100 and 700 nm with a total pore volume of the carrier of at least 1.0 mL / g. The nickel surface must be greater than or equal to 110 m2 per gram of nickel. US 6,673,743 discloses an alumina catalyst having a nickel content between 5 and 75% by weight with a nickel surface greater than 80 m 2 per gram of nickel and a median diameter greater than 10 nm, said catalyst being In the form of particles having a diameter D [3,2] of between 1 and 20 μm, ie it is in powder form. US 5,478,791 discloses an alumina catalyst having a nickel content between 10 and 60% by weight, the nickel particles having a diameter between 15 and 50 nm. The total catalyst volume is between 0.3 and 0.75 g / L and between 20 and 75% of the total pore volume is in pores with a diameter greater than 100 nm. The catalyst also has micropores. Finally, US 4,920,089 discloses an alumina catalyst having a nickel content between 5 and 40% by weight with a nickel surface of between 80 and 300 m 2 per gram of nickel. Alumina exhibits a particular XRD diffractogram. The pore distribution of the catalyst is between 3.5 and 30 nm, and preferably between 4 and 20 nm. In this context, one of the objectives of the present invention is to provide a nickel-phase supported supported catalyst with hydrogenation performance in terms of activity at least as good as the known catalysts of the state of the art.
[0003] More particularly, the invention relates to a supported catalyst comprising a calcined, mainly aluminum oxide support and an active phase comprising nickel, the nickel content being between 5 and 65% by weight of said element relative to the total mass of the catalyst, said active phase does not comprise a group VIB metal, the nickel particles having a diameter of less than or equal to 20 nm, said catalyst having a mesoporous median diameter greater than or equal to 14 nm, a mesoporous volume measured by higher mercury porosimetry or equal to 0.45 ml / g, a total pore volume measured by mercury porosimetry greater than or equal to 0.45 ml / g, a macroporous volume of less than 5% of the total pore volume, said catalyst being in the form of grains having an average diameter of between 0.5 and 10 mm. The applicant has discovered that a catalyst prepared by impregnation of the active phase on an alumina resulting from the calcination of a particular alumina gel prepared according to the method of preparation described below, 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.
[0004] Indeed, the resulting porous distribution of the process for preparing the calcined alumina oxide support derived from a specific alumina gel makes it possible to provide a porosity that is particularly adapted to promoting the diffusion of the reagents in the porous medium and then their reaction with the phase. active. Without being bound by any theory, it appears that the particular textural properties of the catalyst according to the invention, in particular a monomodal porosity with the presence of mesopores of controlled size, makes it possible to obtain a catalyst having hydrogenation performance in terms of activity. at least as good as the known catalysts of the state of the art. The catalyst according to the invention is distinguished by a high mesoporous volume with a median diameter of the high mesopores coupled with a macroporous volume of very low value, or even absent. Indeed, it is well known that although the presence of a macroporous volume can reduce the internal diffusion limitations, it also weakens the mechanical strength of the catalyst. It is therefore important to limit the percentage of macroporous volume with respect to the total pore volume in order to obtain a catalyst having the desired catalytic performance and sufficient mechanical strength. In addition, the presence of a high total pore volume of the catalyst according to the invention makes it possible to impregnate a high content of active phase in a single pass. According to one variant, the median mesoporous diameter of the catalyst is between 18 and 25 nm. According to one variant, the mesoporous volume of the catalyst is between 0.55 ml / g and 0.95 ml / g.
[0005] According to one variant, the macroporous volume of the catalyst is less than 3.5% of the total pore volume. 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 catalyst does not contain pores between 2 and 7 nm.
[0006] Alternatively, the catalyst does not contain micropores. 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.
[0007] DETAILED DESCRIPTION The Catalyst According to the Invention The catalyst according to the invention is in the form of a supported catalyst comprising a calcined predominantly aluminum oxide support and an active phase comprising nickel. The characteristics of the alumina gel which has led to the production of the alumina mainly contained in said support, 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 supported catalyst comprising a calcined predominantly aluminum oxide support and an active phase comprising nickel, 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 or equal to 20 nm, said catalyst having a mesoporous median diameter greater than or equal to 14 nm, a mesoporous volume measured by mercury porosimetry greater than or equal to at 0.45 mL / g, a total pore volume measured by mercury porosimetry greater than or equal to 0.45 mL / g, a macroporous volume of less than 5% of the total pore volume, said catalyst being in the form of grains having a average diameter between 0.5 and 10 mm. The catalyst according to the invention and the support used for the preparation of the catalyst according to the invention exhibit 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 adsorption of nitrogen. "Macropores" means pores whose opening is greater than 50 nm.
[0008] 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. By total pore volume of the catalyst or support used for the preparation of the catalyst according to the invention is meant the volume measured by mercury porosimeter intrusion according to the ASTM D4284-83 standard at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle of 140 °. The anchoring angle 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 intruder porosimeter intrusion. mercury measured on the same sample for a pressure corresponding to 30 psi (about 0.2 MPa). 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. 140 degrees. The value at which the mercury fills all the intergranular voids is fixed at 0.2 MPa, and it is considered that, beyond this, the mercury penetrates into the pores of the sample.
[0010] The macroporous volume of the catalyst or support used for the preparation of the catalyst according to the invention 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 of the invention. apparent diameter greater than 50 nm. The mesoporous volume of the catalyst or support used for the preparation of the catalyst according to the invention is defined as the cumulative volume of mercury introduced at a pressure of between 30 MPa and 400 MPa, corresponding to the volume contained in the pores of apparent diameter. 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 mesoporous median 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 intrusion into the mercury porosimeter. The macroporous median diameter is also defined as being the diameter such that all the pores, among all the pores constituting the macroporous volume, smaller than this diameter constitute 50% of the total macroporous volume determined by intrusion into the mercury porosimeter. . By the specific surface of the catalyst or of the support used for the preparation of the catalyst according to the invention, 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 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, chief editor 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. Characteristics of the support according to the invention The support of the catalyst according to the invention mainly comprises a calcined aluminous porous oxide. Said support has a calcined alumina content greater than or equal to 90% by weight relative to the total weight of said support, optionally supplemented with silica and / or phosphorus to a total content of at most 10% by weight of SiO 2 equivalent and / or or P2O5, 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 by impregnation of the support used for the preparation of the catalyst according to the invention.
[0011] Even more preferably, the predominantly aluminized calcined porous oxide support is alumina. Preferably, the alumina present in said support is a transition alumina such as a gamma, delta, theta, chi, rho or eta alumina, alone or in a mixture. More preferably, the alumina is a gamma, delta or theta transition alumina, alone or as a mixture. The following characteristics of the support correspond to the characteristics of the support used for the preparation of the catalyst according to the invention before impregnation of the active phase. The support used for the preparation of the catalyst according to the invention has a total pore volume greater than or equal to 0.68 ml / g, preferably greater than or equal to 0.70 ml / g, and particularly preferably between 0, 70 and 1.0 mL / g. The support used for the preparation of the catalyst according to the invention advantageously has a macroporous volume of less than 5% of the total pore volume of the support, preferably less than 3.5% of the total pore volume of the support. According to one variant, the support used for the preparation of the catalyst according to the invention has a macroporous volume of less than 0.05 ml / g. The mesoporous volume of the support used for the preparation of the catalyst according to the invention is greater than or equal to 0.68 ml / g, preferably greater than or equal to 0.70 ml / g, and particularly preferably between 0, 70 and 1.0 mL / g. The support used for the preparation of the catalyst according to the invention does not have pores with a diameter of between 2 and 7 nm.
[0012] The median mesoporous diameter of the support used for the preparation of the catalyst according to the invention is greater than or equal to 16 nm, preferably greater than or equal to 18 nm, and particularly preferably between 20 and 25 nm. When macropores are present, the macroporous median diameter of the support is advantageously between 60 and 200 nm, preferably between 60 and 120 nm.
[0013] The support used for the preparation of the catalyst according to the 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 60 and 400 m 2 / g.
[0014] When it is desired to use the catalyst according to the invention in a reaction for the selective hydrogenation of polyunsaturated molecules such as diolefins, acetylenics or alkenylaromates, the support used for the preparation of the catalyst according to the invention advantageously has a BET specific surface area Between 60 and 230 m 2 / g. When it is desired to use the catalyst according to the invention in an aromatic hydrogenation reaction, the support used for the preparation of the catalyst according to the invention advantageously has a B.E.T. between 130 and 400 m2 / g.
[0015] Preferably, the support used for the preparation of the catalyst according to the invention has a low microporosity, very preferably it has no microporosity. Characteristics of the Catalyst The finished catalyst, that is to say with the active phase deposited on the support by any method known to those skilled in the art, as described below, therefore has the textural properties to follow. . The catalyst according to the invention has a total pore volume greater than or equal to 0.45 ml / g, preferably greater than or equal to 0.48 ml / g, and particularly preferably between 0.55 and 0.95 mL / g. The catalyst according to the invention advantageously has a macroporous volume of less than 5% of the total pore volume of the catalyst, preferably less than 3.5% of the total pore volume of the catalyst. According to one variant, the catalyst according to the invention has a macroporous volume of less than 0.05 ml / g.
[0016] The mesoporous volume of the catalyst is greater than or equal to 0.45 ml / g, preferably greater than or equal to 0.48 ml / g, and particularly preferably between 0.55 and 0.95 ml / g. The catalyst according to the invention does not have pores with a diameter of between 2 and 7 nm.
[0017] The mesoporous median diameter of the catalyst is greater than or equal to 14 nm, and preferably greater than or equal to 16 nm, and particularly preferably between 18 and 25 nm. When macropores are present, the macroporous median diameter of the catalyst is advantageously between 60 and 200 nm, preferably between 60 and 120 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.
[0018] When it is desired to use the catalyst according to the invention in a selective hydrogenation reaction of polyunsaturated molecules such as diolefins, acetylenics or alkenylaromates, the catalyst according to the invention advantageously has a B.E.T. between 55 and 170 m2 / g. When it is desired to use the catalyst according to the invention in a reaction for the hydrogenation of aromatics, the catalyst according to the invention advantageously has a B.E.T. between 90 and 250 m2 / g. Preferably, the catalyst has a low microporosity, very preferably it has no microporosity.
[0019] 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 preferred between 10 and 34% by weight. The Ni content is measured by X-ray fluorescence.
[0020] When it is desired to use the catalyst according to the invention in a reaction for selective hydrogenation of polyunsaturated molecules such as diolefins, acetylenics or alkenylaromates, the nickel content is advantageously 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.
[0021] When it is desired to use the catalyst according to the invention in an aromatic hydrogenation reaction, the nickel content is advantageously between 15 and 65% by weight, preferably between 18 and 55% by weight. and more preferably 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 20 nm, preferably between 1.5 and 18 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 the nickel crystallites in oxide form is determined by X-ray diffraction from the width of the diffraction line at the angle θ = 43 ° (i.e. in the crystallographic direction [ 200]) using Scherrer's relation. 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. 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 selected 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.
[0022] The active phase of the catalyst does not comprise any Group VIB metal. It does not include molybdenum or tungsten. Said catalyst according to the invention is in the form of grains having a mean diameter of between 0.5 and 10 mm. The grains may have all the forms known to those skilled in the art, for example the shape of beads (preferably having a diameter of between 1 and 6 mm), extrudates, tablets, hollow cylinders. Preferably, the catalyst (and the support used for the preparation of the catalyst) are in the form of extrudates with an average diameter of between 0.5 and 10 mm, preferably between 0.8 and 3.2 mm and very preferably between 1.0 and 2.5 mm and average length between 0.5 and 20 mm. The term "mean diameter" of the extrudates means the average diameter of the circle circumscribed in the cross-section of these extrusions. The catalyst 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 present invention also relates to a process for preparing said catalyst according to the invention. The catalyst according to the invention 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. 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 shaped and then subjected to heat treatment in order to obtain a calcined aluminum porous oxide support. The calcined aluminous porous oxide support is then impregnated with a solution comprising the salt (s) of the precursor (s) of the active phase, and then dried to obtain a dried catalyst. Then the dried catalyst is optionally subjected to a heat treatment, then generally reduced and subjected to a passivation treatment. 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, aluminate of potassium, 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 forwarding rate of the first step of between 5 and 13%, the rate of progress being defined as the proportion of alumina formed in A1203 equivalent during said first 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 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 precipitation step of the suspension obtained at the end of the heating step b) by adding to the suspension at least one basic precursor 25 selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, nitrate d aluminum, sulfuric acid, ch 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. , 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 Al.sub.2 O.sub.3 equivalent during said second precipitation step relative to the total amount of alumina formed in Al.sub.2 O.sub.3 equivalent at the end of step c) of the preparation process, said step operating at a temperature of temperature 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, 10 e) a step of drying said alumina gel obtained in step d) to obtain a powder, f) a step of shaping the powder obtained at the end of step e) to obtain a raw material g) a step of heat treatment of the green material obtained at the end of step f) at a temperature of between 500 and 1000 ° C., with or without a flow of air containing up to 60 ° C. % by volume of water, to obtain a calcined aluminum oxide support, h) a step of impregnating said support with a solution comprising the salt (s) of the precursor (s) of the nickel-based active phase (I) a step of drying said impregnated support 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 of between 250 and 1000 ° C. C with or without 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 and 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 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 at 5 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 between 20 and 90 ° C, and for a period of 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.
[0023] 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 in admixture in the precipitation step. 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.
[0024] 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 between 8.5 and 10, and very preferably between 8.7 and 9.9.
[0025] 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 acid 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. The first step a) of precipitation is carried out at a temperature of between 20 and 90 ° C, preferably between 20 and 70 ° C, more preferably between 10 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 advance 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 A1203 equivalent during said first or second precipitation step relative to the total amount of alumina formed in equivalent A1203 at the end of two stages of precipitation and more generally at the end of 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. The acidic and basic precursors containing aluminum are therefore 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.
[0026] Step b) Heating According to the invention, said method of preparation comprises a step b) of heating the suspension obtained in step a) at a temperature of between 40 and 90 ° C. for a duration of between 7 and 45.degree. minutes to get an alumina gel.
[0027] 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 between 40 and 90 ° C, preferably between 40 and 80 ° C, preferably between 40 and 7J ° C.
[0028] Said heating step is carried out for a period of between 7 and 45 minutes, and preferably between 7 and 35 minutes. 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 of an 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 aluminum sulphate, aluminum chloride, aluminum nitrate, 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 in such a way as to to get a rate of progress of the second step 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 302 72 8 18 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.
[0029] The acidic precursors comprising aluminum are aluminum sulphate, aluminum chloride and aluminum nitrate. The preferred acidic precursor is aluminum sulphate. 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. 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 acid 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. The second precipitation step is carried out at a temperature between 40 and 90 ° C, preferably between 40 and 80 ° C, and preferably between 45 and 70 ° C, and very preferably between 50 and 70 ° C vs.
[0030] 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 and 40 minutes. The aluminum precursors are also mixed in amounts to provide a slurry containing the desired amount of alumina, depending on the final alumina concentration 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.
[0031] 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 of 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 10 formed in Al 2 O 3 equivalent during said first or second precipitation step relative to the total amount of alumina formed in Al 2 O 3 equivalent at the same time. after the 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.
[0032] Thus, depending on the concentration of alumina referred to after the two stages a) and c) precipitation, generally between 20 and 100 g / l, preferably between 20 and 80 g / l, preferably between 20 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 to the reaction medium and the rate of progress required for each of the precipitation steps. 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.
[0033] By way of example, if working in a 3 L reactor and aiming at 1 L of alumina suspension of final A1203 concentration of 50 g / L, 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 sulphate must be 2.1 ml / min and the flow rate of sodium aluminate is 2.6 ml / min. The mass ratio of sodium aluminate to aluminum sulfate is therefore 1.91. 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. 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.
[0034] 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. and 14%, and very preferably between 7 and 13%, and even more preferably between 7 and 10% and a boehmite particle size between 1 and 35 nm and preferably between 2 to 35 nm. The low degree of dispersibility 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 pelletizing and by the so-called of the drop of oil (dripping). Step e) Drying of the alumina skies In accordance with 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 which will separate the air from the powder. 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.
[0035] Step f) Shaping In accordance with the invention, the powder obtained at the end of the drying step e) is shaped in a step f) to obtain a green material. The term "raw material" means the material shaped and having not undergone heat treatment steps.
[0036] Preferably, said shaping step f) is carried out according to any technique known to those skilled in the art, for example extrusion forming methods, pelletizing, by the method of the drop of oil ( dripping) or by granulating the turntable.
[0037] Very preferably, said forming step f) is carried out by extrusion. A piston extruder can be used through a die having the desired diameter, typically between 0.5 and 10 mm. The extrudates generally have an average diameter of between 0.5 and 10 mm, preferably 0.8 and 3.2 mm, and very preferably between 1.0 and 2.5 mm, and an average length of between 10 and 10 mm. , 5 and 20 mm. The extrudates may advantageously be in the form of cylindrical, multilobed, trilobed or quadrilobed extrudates. Preferably the shape will be trilobed or quadrilobed. Any other element, for example silica in the form of a solution or a silicic precursor emulsion, may be introduced during the shaping.
[0038] Step c1) Heat treatment According to the invention, the green material obtained at the end of the shaping step f) then undergoes a step g) of heat treatment at a temperature of between 500 and 1000 ° C. in the presence or absence of air flow containing up to 60% water volume.
[0039] Preferably, said heat treatment step g) operates at a temperature of between 540 and 850 ° C. Preferably, said heat treatment step g) operates for a duration of between 2 and 10 hours. The heat treatment step may be preceded by drying at a temperature of between 50 ° C. and 200 ° C., according to any technique known to those skilled in the art.
[0040] The term "heat treatment" 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 without presence or with presence of water can be realized.
[0041] In the presence of water, 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 heat treatment step g) allows the transition of the alumina gel, also called boehmite, to a calcined 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 step g) of heat treatment. Step h) Impregnation of the active phase According to step h) of the process according to the invention, the aluminized porous aluminum oxide support is impregnated with a solution comprising the salt (s) of the precursor (s) of the phase active nickel based.
[0042] The active phase is provided by one or more solutions containing at least nickel. 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 aluminum porous oxide. Preferably, nickel precursor is advantageously used, nickel nitrate, nickel chloride, nickel acetate or nickel hydroxycarbonate. Very preferably, the nickel precursor is nickel nitrate or nickel hydroxycarbonate. 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 a solution of ammonium carbonate or ammonium carbonate. ammonium hydrogencarbonate. The amounts of the nickel precursor (s) introduced into the solution are chosen such that the total nickel content is between 5 and 65 wt., Preferably between 8 and 55 wt.%, Preferably between 10 and 40 wt. 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 at the time of this step: When it is desired to introduce phosphorus, a solution of phosphoric acid may be introduced into the impregnating solution. 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 salt is advantageously used as precursor. conventional precursor. 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. The impregnation of the active phase can be carried out according to all the methods known to those skilled in the art, in particular by dry impregnation. Preferably, the nickel and optionally at least one additional element such as an additional metal selected from Group VIII metals, Group IB metals and / or tin, phosphorus or an additive such as an agent Chelating agents of organic nature are deposited by dry impregnation of their associated precursors on the oxide support according to the invention.
[0043] The deposition may be carried out via a single step of dry impregnation of the oxide support according to the invention via the use of a solution containing simultaneously at least one nickel compound, and possibly at least one additional element. . The deposition may also be advantageously carried out via at least two cycles of dry impregnation. The different elements can thus be advantageously impregnated successively or one of the elements can also be impregnated into several sequences. One of the impregnations which is carried out can in particular make it possible to introduce an organic compound in addition to the active phase of the catalyst. In these cases, each impregnation is advantageously followed by drying and optionally heat treatment. The drying can be carried out at a temperature between 15 and 250 ° C, preferably between 80 and 200 ° C, generally for a period of between 10 minutes and 24 hours. The heat treatment can be carried out at a temperature between 200 and 1000 ° C, preferably between 250 and 750 ° C, brilliantly for a period of between 15 minutes and 10 hours. Step i) Drying of the impregnated support According to the invention, the impregnated support obtained at the end of step h) of impregnation of the active phase undergoes a drying step i) at a temperature of between 15 and less than 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 further heat treatment step j) at a temperature of between 250 and 1000 ° C and preferably between 250 and 750 ° C for a period of time typically between 15 minutes and 10 hours, with or without water. The term "heat treatment" means the temperature treatment respectively without presence or in the presence of water. In the latter case, the contact with the steam can take place at atmospheric pressure ("steaming") or autogenous pressure (autoclaving). 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 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. Step k) Reduction by a reducing agent Prior to 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 gas. reducing agent 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 loading the catalyst into the hydrogenation reactor. Said step k) of reducing treatment can be carried out on the catalyst which 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 the 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 catalytex has been passivated beforehand, the reducing treatment is generally carried out at a temperature between 120 and 350 ° C, preferably between 150 and 350 ° C.
[0044] The duration of the reducing treatment is generally between 2 and 40 hours, preferably between 3 and 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. 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, still 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 carried out 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" according to 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 implementation 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 chosen 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 HOC2H4-SS-C2H4-OH (often called DEODS). The sulfur content is generally between 0.1 and 2% by weight of said element relative to the weight of the catalyst.
[0045] 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 lower temperature reducing treatment generally between 120 and 350 ° C is then generally performed. 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 selective hydrogenation of polyunsaturated compounds such as diolefins, acetylenics or alkenylaromatics, also called styrenics. Monounsaturated organic compounds such as, for example, ethylene and propylene, are 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 the like. 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 compounds or styrenic or indene. These polyunsaturated compounds are highly reactive and lead to spurious reactions in the polymerization units. It is therefore necessary to eliminate them before valuing these cuts. 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.
[0046] 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. 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.), styrene 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 of pyrolysis gasoline generally has the following composition: 5 to 25 wt% paraffins, 40 to 70 wt% aromatics, 5 to 20 wt% monoolefins, 5 to 40 wt% 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.
[0047] The selective hydrogenation process according to the invention aims to eliminate 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, the aim is to eliminate butadiene, vinylacetylene (VAC) and butyl, in the case of a C5 cut, the aim is to eliminate the 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 compounds and indenics are partially hydrogenated to corresponding aromatic compounds by avoiding the hydrogenation of aromatic rings. The technological implementation of the selective hydrogenation process is carried out, for example, by injection, in ascending or descending current, of the polyunsaturated hydrocarbon feedstock and hydrogen in at least one fixed bed reactor. 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 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 hydrogen stream can be introduced at the same time as the feed to be hydrogenated and / or at one or more different points of the reactor. 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. In fact, a reaction in the liquid phase makes it possible to lower the energy cost and to increase the catalyst cycle time.
[0048] 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 0.1 and 10 and at a volume velocity hourly VVH (defined as the ratio of the volume flow rate of charge to the volume of the catalyst) of between 0.1 and 200 h -1 for a liquid charge, between 100 and 15 000 h -1 for a gaseous charge, a charge of hydrocarbons 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.
[0049] 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.
[0050] 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 the aromatic compounds of petroleum or petrochemical cuts by means of a hydrogenation process. conversion of aromatic rings to naphthenic rings. The hydrocarbon feedstock treated in the aromatic hydrogenation process has a final boiling point of less than or equal to 650 ° C, generally between 20 and 650 ° C, and preferably between 20 and 450 ° C, and in accordance with 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, coking, hydrocracking distillates, and 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. by 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) nuclei such as than 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.
[0051] 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 0.5 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 less than or equal to 650 ° C.
[0052] The hydrogen flow rate is adjusted in order to dispose of it in sufficient quantity to theoretically hydrogenate all the polyunsaturated compounds and to maintain an excess of hydrogen at the reactor outlet. The conversion of 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%. aromatic or polyaromatic compounds 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 charge. 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. The hydrogenation of the benzene-containing feedstock 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 between 0.1 and 10 and at a VVH hourly volume velocity between 0.05 and 50 h -1, preferably between 0.5 and 10 h -1. The conversion of benzene is generally greater than 50 mol%, preferably greater than 80 mol%, more preferably greater than 80 mol%. 90 mol% and particularly preferably greater than 98 mol%. The invention is illustrated by the following examples. EXAMPLES 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 and C is prepared by dissolving 46.1 g of nickel nitrate 3025728 34 (NiNO3, supplier Strem Chemicals®) 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 Catalyst A According to the Invention Catalyst A according to the invention is prepared by dry impregnation of solution S with Ni precursors on Al alumina. A content of 20% by weight is sought. nickel relative to the total mass of the catalyst. The alumina Al synthesis according to the invention is carried out in a seven-stage 5 L reactor, named below a) to g). The concentration of the acidic and basic alumina precursors is as follows: aluminum sulphate Al2 (SO4) 3 at 102 g / L in Al2O3 and sodium aluminate NaAlOO 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 Al2 (SO4) 3 aluminum sulphate and NaAl10O sodium aluminate 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 from 30 ° C to 70 ° C in 20 to 30 minutes. c) A second precipitation of aluminum sulphate Al2 (SO4) 3 and NaAl100 sodium aluminate in 30 minutes at 70 ° C, pH = 9.1 and with a 90% feed rate. 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) The dried alumina gel from step e) is shaped using a "Brabender" type kneader with an acid level of 3% (total acid level, expressed as relative to dry alumina), a neutralization rate of 200% and acid and basic fire losses of 62% and 64% respectively. Then the extrusion is carried out on a piston extruder through a trilobal die with a mean diameter of 2.1 mm. After extrusion, the extrudates are dried overnight at 80 ° C. g) The extrudates obtained at the end of step f) are then calcined at 750 ° C. under an air flow of 1 L / h / g of alumina at 750 ° C. for 2 hours (rising ramp at 5 ° C.). temperature of 5 ° C / min). Alumina A1 is obtained. The characteristics of alumina Al thus obtained are reported in Table 1 below. Alumina Al does not contain pores with a diameter of between 2 and 7 nm. Table 1: Properties of alumina Al (according to the invention), and B1 and Cl (comparative) ALUMINES Al B1 Cl According Comparative Comparative the invention Surface B.E.T. (m2 / g) 156 269 298 Total pore volume (mL / g) 0.85 0.64 0.60 Mesoporous volume (mL / g) 0.83 0.61 0.57 Median mesoporous diameter (nm) 21 9, Macroporous volume (mL / g) 0.02 0.03 0.03 Macroporous volume (% of total pore volume) Microporous volume (mL / g) Catalyst A is then prepared by dry impregnation of solution S of Ni precursors, described in Example 1, on alumina Al according to the three steps, named below h) to i): 3025728 h) Dry impregnation of alumina Al in adding dropwise a volume of 11.5 ml of solution S to a mass of 10.5 g of alumina A1 for a period of 10 minutes. i) A drying of the catalytic precursor obtained at the end of step h) in an oven at 120 ° C overnight. j) Heat treatment by calcination of the dried catalyst under a flow of air of 1 L / hr / g of catalyst, at 450 ° C for 2 hours (ramp of 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 2 below. The calcined catalyst A does not contain pores with a diameter of between 2 and 7 nm. TABLE 2 Properties of catalysts A (according to the invention), and B and C (comparative CATALYSTS ABC According Comparative Comparative invention Ni (% wt) 20.3 21.5 21.0 BET surface (m2 / g) 117 188 206 Total pore volume (mL / g) 0.64 0.44 0.43 Mesoporous volume (mL / g) 0.62 0.41 0.40 Median mesoporous diameter (nm) 19 9 16 Macroporous volume (mL / g) ) 0.02 0.03 0.03 Macroporous volume (% of total pore volume) 3 7 7 Microporous volume (mL / g) 0 0 0 Size of NiO crystallites (nm) 15.2 14.1 11.0 3025728 EXAMPLE 3 Preparation of catalyst B having a different porous distribution (comparative) Catalyst B is prepared by dry impregnation of solution S with Ni precursors, aiming at a content of 20% by weight of nickel relative to the total mass of the product. B1 alumina catalyst having a porous distribution different from that of alumina A1 described in Example 2 above The characteristics of this alumina B1 are reported in Table 1. In particular, this alumina B1 has a mesoporous median diameter much lower than that of alumina Al and a total pore volume and a mesoporous volume lower than those of alumina A1. Catalyst B is then prepared by dry impregnation of solution S of Ni precursors, described in Example 1, on alumina B1. On this alumina of small pore volume, two successive impregnations were necessary to achieve Ni content of about 20% by weight; the sequence of the three steps h) to i) of Example 2 described above, was then repeated twice (according to the sequence h, i, j, h, i, j). The first impregnation stage makes it possible to obtain a content of 14.9% by weight of nickel, the second impregnation stage makes it possible to reach a content of 21.5% by weight of nickel relative to the total mass of the catalyst. . For each step, the operating conditions are strictly identical to those described in Example 2 above. The calcined catalyst B thus obtained is obtained. The characteristics of the calcined catalyst B thus obtained are given in Table 2. It has a mesoporous median diameter much smaller than that of the catalyst A, as well as a total pore volume, a mesoporous volume and NiO crystallites smaller than those of catalyst A. Example 4: Preparation of catalyst C having a different porous distribution (comparative) Catalyst C is prepared by dry impregnation of solution S of Ni precursors aiming at a content of 20% by weight nickel based on the total weight of the catalyst on a Cl alumina having a porous distribution still different from that of the Al alumina described in Example 2 above. The characteristics of this Cl alumina are shown in Table 1. In particular, this Cl alumina does not have a total pore volume and a mesoporous volume lower than those of Al alumina but a median mesoporous diameter close to that of alumina. Al. Catalyst C is then prepared by dry impregnation of solution S of precursors of Ni, described in Example 1, on alumina Cl. On this alumina of small pore volume, two successive impregnations were necessary to reach a content in Ni of about 20% by weight; the sequence of the three steps 10 h) to i) of Example 2 described above was then repeated twice (according to the sequence h, i, j, h, i, j). The first impregnation step makes it possible to obtain a content of 13.3% by weight of nickel, the second impregnation stage makes it possible to reach a content of 21.0% by weight of nickel relative to the total mass of the catalyst. For each step, the operating conditions are strictly identical to those described in Example 2 above. The calcined catalyst C is thus obtained. The characteristics of the calcined catalyst C thus obtained are given in Table 2. It has a total pore volume and a mesoporous volume and crystallites of NiO smaller than those of the catalyst A.
[0053] EXAMPLE 5 Evaluation of the Catalytic Properties of Catalysts A, B and C in Selective Hydrogenation of a Styrene-Isoprene-containing Mixture Catalysts A, B and C described in the above examples were tested for and the reaction of selectively hydrogenating 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 ) (VWR® supplier, purity> 99% chromanorm HPLC). This feed also contains very low sulfur compounds: 10 ppm wt sulfur introduced as pentanethiol (Fluka® supplier, purity> 97%) and 100 ppm wt sulfur introduced as 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.
[0054] The selective hydrogenation reaction is carried out in a 500 ml stainless steel autoclave equipped with a magnetic drive mechanical stirrer and capable of operating at a maximum pressure of 100 bar (10 MPa) and temperatures of 5 ° C. and 200 ° C. Prior to its introduction into the autoclave, a quantity of 3 mL of the catalyst is reduced ex situ under a flow of hydrogen of 1 L / h / g of catalyst, at 400 ° C. for 16 hours (ramp for raising the temperature 1 ° C / min), then it is transferred to the autoclave, protected from the air. After addition of 214 mL of n-heptane (supplier VWR®, purity> 99% chromanorm HPLC), the autoclave is closed, purged, then pressurized under 35 bar (3.5 MPa) of hydrogen, and brought to temperature. 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.
[0055] The catalytic activities measured for catalysts A, B and C are reported in Table 3 below. They are related to the catalytic activity measured for catalyst A (AHypi).
[0056] Table 3: Comparison of performances in selective hydrogenation of a mixture containing styrene and isoprene (AHypi) and hydrogenation of toluene (AHYD2). Catalyst Conform Size of AHYD1 AHYD2 Crystallites of (%) (%) NiO (nm) A Yes 15.2 100 100 B No 14.1 48 41 C No 11.0 63 54 This shows the improved performance of Catalyst A prepared according to 10 l invention and in particular the impact of its specific textural properties. Indeed, catalysts B and C, although having NiO crystallites smaller than those of catalyst A, have poorer catalytic performance. The presence of mesopores of controlled size is therefore necessary to obtain the improved performances of the catalyst A.
[0057] Example 6: Evaluation of the Catalytic Properties of Catalysts A, B and C in Hydrogenation of Toluene Catalysts A, B and C described in the above examples are also tested for the hydrogenation reaction of toluene.
[0058] The selective hydrogenation reaction is carried out in the same autoclave as that described in Example 5. 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 VWR®, purity> 99% chromanorm HPLC), the autoclave is closed, purged and then pressurized under 35 bar (3.5 MPa) of hydrogen, and brought to temperature. test equal to 80 ° C. At time t = 0, about 26 g of toluene (SDS® supplier, 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 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 fully 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.
[0059] The catalytic activities measured for Catalysts A, B and C are reported in Table 3. 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]
CLAIMS1.A supported catalyst comprising a calcined, predominantly aluminized aluminum support and an active phase comprising nickel, 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 any metal group VIB, nickel particles having a diameter less than or equal to 20 nm, said catalyst having a mesoporous median diameter greater than or equal to 14 nm, a mesoporous volume measured by mercury porosimetry greater than or equal to 0.45 ml / g a total pore volume measured by mercury porosimetry greater than or equal to 0.45 ml / g, a macroporous volume of less than 5% of the total pore volume, said catalyst being in the form of grains having a mean diameter of between 0.5 and 10 mm.
[0002]
The catalyst according to claim 1, wherein the mesoporous median diameter of the catalyst is between 18 and 25 nm.
[0003]
3. The catalyst according to claim 1 or 2, wherein the mesoporous volume of the catalyst is between 0.55 mL / g and 0.95 mL / g.
[0004]
4.Catalyst according to claims 1 to 3, wherein the macroporous volume of the catalyst is less than 3.5% of the total pore volume.
[0005]
5.Catalyst according to claims 1 to 4, wherein the nickel content is between 10 and 34% by weight of said element relative to the total mass of the catalyst.
[0006]
6.Catalyst according to claims 1 to 5, which does not contain pores with a diameter of between 2 and 7 nm.
[0007]
7.Catalyst according to claims 1 to 6, which does not contain micropores.
[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 acid precursors comprises aluminum, the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the medium. 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 first stage progress rate of between 5 and 13%, the 'advancement being defined as being the a 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 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, chloro acid ydrique 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, And the flow rate of the aluminum-containing acidic and basic precursor (s) is adjusted so as to obtain a progress rate of 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 Al 2 O 3 at the end of step c) of the preparation process, said step operating at a temperature of between 40.degree. and 90 ° C and for a period of time 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, 302 5 72 8 44 e) a drying step of said alumina gel obtained in step d) to obtain a powder, f) a step of shaping the powder obtained at the end of step e) to obtain a raw material, 5 g ) a heat treatment step of the raw material obtained at the end of step f) at a temperature of between 500 and 1000 ° C., with or without a flow of air containing up to 60% by volume water, to obtain a calcined alumina support, h) a step of impregnating said support with a solution comprising the salt (s) of the precursor (s) of the active phase based on nickel, i ) a step of drying said impregnated support at a temperature 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 no water. 15
[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]
The process according to 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. The method of claims 8 to 10, wherein the rate of advance of the first precipitation step a) is between 6 and 12%.
[0012]
The process according to claims 8 to 11, wherein the acid precursor of steps a) and c) is selected from aluminum sulphate, aluminum chloride and aluminum nitrate and wherein the basic precursor of Steps a) and c) are selected from sodium aluminate and potassium aluminate.
[0013]
13. Hydrogenation process in which the catalyst according to 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 feed containing compounds. polyunsaturated and / or aromatic so as to obtain an effluent that is at least partially hydrogenated. 3025728 45
[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 volume velocity of between 0.1 and 200 h -1 for a liquid feed, of between 100 and 15000 h -1 for a gaseous feed, of a hydrocarbon feedstock. 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. Hydrogenation process according to claim 13, in which 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 hydrogen / compound mole ratio. aromatics to be hydrogenated) between 0.1 and 10 and at an hourly space velocity of between 0.05 and 50 h-1, a hydrocarbon feedstock containing aromatic compounds and having a final boiling point of less than or equal to at 650 ° C.

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同族专利:

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公开号 | 公开日

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EP3191221B1|2020-01-01|

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EP3191221A1|2017-07-19|

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US20170259249A1|2017-09-14|

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JP6573664B2|2019-09-11|

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SA517381034B1|2021-06-06|

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CN106660905B|2021-03-12|

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US10307738B2|2019-06-04|

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WO2016037830A1|2016-03-17|

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DK3191221T3|2020-03-23|

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JP2017533085A|2017-11-09|

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CN106660905A|2017-05-10|

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FR3025728B1|2018-04-20|

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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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FR1458543A|FR3025728B1|2014-09-11|2014-09-11|MESOPOROUS CATALYST BASED ON NICKEL AND ITS USE IN HYDROGENATION.|

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FR1458543|2014-09-11|FR1458543A| FR3025728B1|2014-09-11|2014-09-11|MESOPOROUS CATALYST BASED ON NICKEL AND ITS USE IN HYDROGENATION.|

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US15/509,873| US10307738B2|2014-09-11|2015-08-21|Nickel-based mesoporous catalyst and use thereof in hydrogenation|

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EP15759689.1A| EP3191221B1|2014-09-11|2015-08-21|Mesoporous nickel-based catalyst and use thereof for hydrocarbon hydrogenation|

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PCT/EP2015/069223| WO2016037830A1|2014-09-11|2015-08-21|Mesoporous catalyst made from nickel and use of same in hydrocarbon hydrogenation|

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DK15759689.1T| DK3191221T3|2014-09-11|2015-08-21|MESOPOROUS NICKEL-BASED CATALYST AND ITS APPLICATION FOR HYDROGENATION OF CARBON HYDROIDS|

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CN201580048722.7A| CN106660905B|2014-09-11|2015-08-21|Nickel-based mesoporous catalysts and their use in hydrogenation|

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JP2017513474A| JP6573664B2|2014-09-11|2015-08-21|Nickel-based mesoporous catalyst and its use in hydrogenation|

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SA517381034A| SA517381034B1|2014-09-11|2017-03-05|Nickel-Based Mesoporous Catalyst and Use Thereof in Hydrogenation|