Hydrotreating catalyst preparation process

Abstract

The invention relates to a process for preparing a hydrotreating catalyst, the process comprising: mixing catalyst fines of a hydrotreating catalyst with at least a binder to form a mixture to provide a first hydrotreating catalyst containing a Group VI metal and a Group VIII metal, typically a spent regenerated catalyst; shaping the mixture to form a shaped mixture, the mixture containing at least 60 wt.% of the catalyst fines based on the dry weight of the mixture; heat-treating the shaped mixture; and rejuvenating the shaped mixture. The invention further relates to a hydrotreating catalyst obtained by the process, and to a process for hydrotreating a hydrocarbon feed using the hydrotreating catalyst.

Description

[Technical Field]

[0001] I. FIELD OF THE INVENTION The present invention relates to a process for the preparation of a hydrotreating catalyst. The invention further relates to a hydrotreating catalyst obtainable by this process and to a process for hydrotreating a hydrocarbon feed using said hydrotreating catalyst. [Background technology]

[0002] II. Description of the Background Art Generally, the purpose of catalytic hydrotreating a hydrocarbon-containing feed is to remove impurities. Common impurities include sulfur and nitrogen compounds. At least partial removal of such impurities from the feed reduces the emission of environmentally harmful sulfur and nitrogen oxides when the final product is combusted. Furthermore, sulfur and nitrogen compounds are poisonous to many of the catalysts used in the petroleum industry to convert feeds into usable products. Examples of such catalysts include cracking catalysts, hydrocracking catalysts, and reforming catalysts. Therefore, feeds are typically subjected to catalytic hydrotreating before being processed, for example, in a cracking unit.

[0003] Catalytic hydrotreating involves contacting a feed with hydrogen at elevated temperatures and pressures in the presence of a hydrotreating catalyst. In this process, sulfur and nitrogen compounds present in the feed are converted to easily removable hydrogen sulfide and ammonia in processes called hydrodesulfurization and hydrodenitrogenation, respectively.

[0004] Generally, hydrotreating catalysts are composed of a support on which a Group VI metal component and a Group VIII metal component are supported. The most commonly used Group VI metals are molybdenum and tungsten, while cobalt and nickel are traditional Group VIII metals. Phosphorus may also be present in the catalyst. Hydrotreating catalysts are usually shaped, for example in the form of extrusions.

[0005] Prior art processes for preparing these catalysts are characterized in that the support material is complexed with the hydrogenation metal components, for example by impregnation, and the complex is then calcined to convert the metal components to their oxides. Prior to use in hydroprocessing, the catalyst is generally presulfided to convert the hydrogenation metals to sulfides.

[0006] The preparation of hydrotreating catalysts is an energy-intensive process that requires the use of large amounts of expensive natural resources such as molybdenum, cobalt, nickel, and aluminum.

[0007] A potential problem during catalyst preparation during catalyst molding is the formation of unusable catalyst by-products. These unusable materials include, for example, catalyst fines resulting from support production, fresh catalyst production, catalyst regeneration, or damaged extrudates that do not meet the length specifications required by the purifier to prevent excessive pressure drop within the unit. This formation of unusable catalyst material contributes to inefficient use of raw materials. There is a need to improve resource use and reduce waste.

[0008] Spent catalysts, i.e., used catalysts that have reacted in hydrotreating processes and can no longer perform catalytic functions, are typically disposed of in landfills. Regeneration of used catalysts, which involves thermal treatment to burn off coke and / or sulfur deposits, can only restore the activity of the used catalyst to a certain extent. Furthermore, mechanical wear of the catalyst, mechanical damage during material processing and / or transport within the equipment, and repeated harsh reaction conditions during hydrotreating and / or regeneration can compromise the desired extrudate length. The reduction in extrudate length due to continuous hydrotreating / regeneration treatments inevitably increases the pressure loss within the reactor, which is unacceptable for refiners constrained by hydraulic pressure and acceptable pressure profiles. Therefore, reactivation of used catalysts is limited, and refiners remain heavily dependent on a continuous supply of freshly prepared hydrotreating catalysts.

[0009] In addition to regeneration, spent catalysts may also undergo rejuvenation processes, which involve contacting the regenerated spent catalyst with organic additives and / or acids. These rejuvenation processes can further restore the activity of the spent catalyst. However, the rejuvenation process cannot be repeated indefinitely to restore the regenerated catalyst. After a certain number of rejuvenations, the catalyst can no longer be used in hydrotreating processes and must be recycled to recover the metals.

[0010] US 4,107,087 describes a method for preparing a hydrotreating catalyst from silica / alumina catalyst fine particles, the method comprising the steps of: A. adding 1.0 to 15.0 wt. % citric acid to an aqueous slurry of the silica / alumina catalyst fine particles, resulting in silica / alumina hydrotreating catalyst fine particles impregnated with: (1) a metal selected from the group consisting of iron, cobalt, nickel, palladium, and platinum, and (2) a metal selected from the group consisting of chromium, molybdenum, tungsten, selenium, and tellurium; and B. mixing, filtering, drying, extruding, and calcining to form a hydrotreating catalyst. The fine particles are generated by attrition and breakage during the preparation of fresh catalyst or are recovered from regenerated or spent catalyst. It has been reported that the addition of citric acid to large amounts of catalyst fine particles allows their incorporation into catalyst formulations without impairing important physical properties.

[0011] In their paper "Preparation of Heavy Oil Hydrotreating Catalyst from Spent Residue Hydroprocessing Catalysts" in Catalysis Today 130 (2008) 421-428, M. Marafi et al. described a recycling process for vanadium-rich spent hydrotreating catalysts. Spent catalyst extrudates containing different levels of V, Mo, and Ni on Al2O3 were subjected to different treatments, including washing, decoking, acid leaching, and hydrothermal treatment. The treated spent catalyst was crushed and ground into fine powder. The spent catalyst powder was mixed with boehmite in different ratios, followed by peptide synthesis, kneading, extrusion, drying, and calcination to prepare new hydrotreating catalysts. Acid leaching and hydrothermal leaching significantly reduced the metal content but were also beneficial for removing V from the pore openings and unblocking the pores. It has been found that, for spent catalysts treated in this way, 40-60 wt% spent catalyst can be added to boehmite to prepare new catalysts with large pores, significantly higher surface area and pore volume, and higher activity for promoting HDM and HDS reactions. The drawback of this method is that, while optimized to reduce the adverse effects of vanadium and provide some activity recovery, the loss of active metals is significant, resulting in lower than desired activity recovery rates. Furthermore, leaching and recovery of leached metals require significantly more processing steps.

[0012] WO2012021386 describes a method for preparing a hydrotreating catalyst from spent catalyst fines. The catalyst fines used in the present invention are prepared from either waste hydrotreating catalyst, regenerated hydrotreating catalyst, or recycled but unused hydrotreating catalyst. The method includes forming a shaped support from inorganic oxide powder and catalyst fines, where the catalyst fines are present on the shaped support in an amount ranging from about 50 wt% of the shaped support, drying and calcining the shaped support, incorporating a metal-containing solution into the shaped support to form a metal-containing support, drying the metal-containing support to provide a dry metal-containing support having a volatile matter content ranging from 1 to 20 wt% LOI, incorporating a polar additive into the dry metal-containing support to provide an additive-impregnated composition, and incorporating a chelating agent into either the shaped support or the dry metal-containing support. A problem with using crushed catalyst fines in preparing new catalysts is that a larger proportion of the catalyst's pore volume may be contributed to by the catalyst's macropores (diameters 350 Å and larger) than would be the case if the new catalyst were prepared without crushed catalyst fines, i.e., from virgin materials. This higher proportion of macropore volume can contribute to reduced catalytic activity. Therefore, the amount of fines used in the catalyst is less than 50 wt%, most preferably between 15 wt% and 35 wt%.

[0013] Tightening regulations and growing societal demands for a more sustainable industry are driving the need for improved reactivation processes to keep catalysts operational for longer periods. There is also a need for more efficient metal recycling processes to reduce the use of dwindling natural resources and reduce waste in landfills. The oil industry is also under pressure to reduce its carbon footprint.

[0014] It is an object of the invention to address one or more of the above mentioned problems.

[0015] It is also an object of this invention to provide an improved process for reactivating spent hydroprocessing catalysts or unusable fresh catalyst material, and to provide a process for preparing hydroprocessing catalysts from such spent hydroprocessing catalysts or unusable fresh catalyst material.

[0016] In a further aspect, the present invention relates to hydrotreating catalysts obtainable by the improved process and their use in hydrotreating processes. Summary of the Invention

[0017] III. Summary of the Invention The invention is defined in the independent claims, while further aspects of the invention are set out in the dependent claims and the description below.

[0018] According to the present invention, there is provided a process for preparing a hydrotreating catalyst, the process comprising: a) providing a first hydrotreating catalyst comprising a Group VI metal and a Group VIII metal selected from the group consisting of fresh catalyst, regenerated catalyst, rejuvenated catalyst, fresh catalyst fines, regenerated or rejuvenated catalyst fines, or mixtures thereof; b) grinding the hydrotreating catalyst to form catalyst fines, unless the first hydrotreating catalyst already consists of fresh, regenerated, or rejuvenated catalyst fines, or a mixture thereof; c) the mixture comprises at least 60 wt. % catalyst fines, based on the dry weight of the mixture, optionally at least partially combining mixing and grinding, and optionally after grinding during mixing, adding a first hydroprocessing catalyst consisting of fresh catalyst fines, regenerated catalyst fines, or rejuvenated catalyst fines, and mixing the catalyst fines with at least a binder to form a mixture; d) shaping the mixture; e) heat treating the shaped mixture; f) and contacting the heat-treated molded mixture with a rejuvenating agent.

[0019] In a preferred embodiment, the process further comprises step g) of contacting the heat-treated shaped mixture with a solution comprising a Group VI and / or Group VIII metal and optionally a phosphorescent compound, which step g) may be carried out before, during or after step f), or the Group VI and / or Group VIII metal is added to the mixture before shaping the mixture.

[0020] In a preferred embodiment, the solution contains Group VI and / or Group VIII metals in amounts such that, after contact, the heat-treated shaped mixture is at least 90 wt. %, preferably at least 95 wt. %, and more preferably at least 98 wt. % of the metal concentration, expressed as weight percent (wt. %) of the metal oxide in the first hydrotreating catalyst, thereby restoring as much activity as possible to the original fresh hydrotreating catalyst from which the catalyst particles were derived. In step g), the metals are preferably added as follows: The catalyst contains 5-40 wt. % of a Group VI metal, calculated as trioxide, preferably 10-38 wt. %, more preferably 15-35 wt. %; 1-10 wt. % of a Group VIII metal, calculated as oxide, preferably 2-8 wt. %; and preferably 1-10 wt. % of phosphorus, calculated as P2O5. An advantage of this invention is that relatively small amounts of metal or phosphorus need to be added, and it is easier to add the metal and rejuvenator in one step rather than two or more successive impregnation steps.

[0021] In a preferred embodiment, step g) of contacting the heat-treated shaped mixture with a solution comprising a group VI and / or VIII metal is carried out during step f), preferably the solution comprising a group VI and / or VIII metal also comprising a rejuvenating agent.

[0022] In a preferred embodiment, the first hydrotreating catalyst comprises a regenerated catalyst obtained by regenerating a spent catalyst. Preferably, the first hydrotreating catalyst comprises a low level of metal contamination, in particular, the amount of vanadium on the catalyst is less than 2 wt%, preferably less than 1 wt%.

[0023] In another preferred embodiment, the mixture comprises at least 70 wt%, preferably at least 80 wt%, more preferably at least 85 wt%, even more preferably at least 90 wt%, and most preferably at least 95 wt% catalyst fines, based on the dry weight of the mixture.

[0024] In another preferred embodiment, the binder comprises one or more selected from the group consisting of inorganic oxides, preferably alumina, silica, silica-alumina, magnesium, combinations thereof, salts thereof, and clays, preferably alumina or alumina-silica, most preferably gamma-alumina, the salts of which may have inorganic or organic anions.

[0025] In a preferred embodiment, the binder comprises a material similar to the binder material in the first hydrotreating catalyst, and therefore the binder in the mixture is the same as the support material or binder material of the first hydrotreating catalyst.

[0026] In another preferred embodiment, the catalyst fines have a D50 particle size of less than 200 μm, preferably less than 100 μm, more preferably less than 50 μm, even more preferably less than 30 μm, and preferably greater than 1 μm, more preferably greater than 2 μm, even more preferably greater than 4 μm. If the first hydrotreating catalyst does not have this preferred D50 particle size, it is crushed to form catalyst fines having a D50 particle size in the stated range.

[0027] In a preferred embodiment, the catalyst fines in the mixture have a D90 particle size of less than 500 μm, preferably less than 200 μm, more preferably less than 100 μm, and even more preferably less than 80 μm. The D90 is preferably greater than 1 μm, more preferably greater than 2 μm, and even more preferably greater than 4 μm.

[0028] In a preferred embodiment, the process according to the invention further comprises an ageing step h) after the rejuvenation step f), the ageing being preferably carried out at a temperature of 20-100° C., preferably 30-80° C., for a time preferably less than 18 hours, preferably less than 15, 10, 7, 4 hours, or even less than 2 hours. In one preferred embodiment, the ageing is carried out for a time of 0.5-2 hours, preferably 0.5-1 hour.

[0029] In yet another preferred embodiment, the rejuvenating agent reduces the crystalline fraction of the metal oxide in the heat-treated molding mixture, preferably by at least 20%, preferably by at least 30%, or more preferably by at least 40%.

[0030] In a preferred embodiment, the rejuvenating agent comprises a complexing agent, preferably a carboxylic acid containing at least one carboxyl group and 1 to 20 carbon atoms.

[0031] In the most preferred embodiment, the complexing agent is citric acid or lactic acid.

[0032] In another preferred embodiment, the rejuvenating agent also contains an organic additive, which is preferably selected from the group consisting of compounds containing at least two hydroxyl groups and 2 to 10 carbon atoms per molecule, and ethers or polyethers of these compounds. In this context, the OH group in a carboxylic acid is not considered to be a hydroxyl group. Preferably, the rejuvenating agent is a combination of lactic acid or citric acid with the organic additive.

[0033] The invention further relates to a hydrotreating catalyst obtainable by the steps according to the invention.

[0034] In a preferred embodiment, the hydrotreating catalyst obtained by the process according to the present invention comprises a total pore volume of 0.2 to 1.0 mL / g, preferably 0.3 to 0.7 mL / g, more preferably 0.3 to 0.6 mL / g.

[0035] The hydrotreating catalyst obtained according to the process of the present invention preferably has a typical macropore volume of 0.005 to 0.3 mL / g, preferably the macropore volume is less than 0.1 mL / g, preferably less than 0.06 mL / g. Pores with a diameter of more than 100 nm are considered macropores herein.

[0036] The hydrotreating catalyst obtained by the process according to the present invention preferably has a hydrotreating capacity of 100 to 300 m 2 The hydrotreating catalyst preferably has a side crush strength (SCS) of at least 2 lbs / mm, more preferably at least 3, and even more preferably at least 4 lbs / mm.

[0037] If additional metals are added to the catalyst as described above, the total pore volume and macropore volume of the heat-treated shaped mixture used as a support for the catalyst can be higher than that of the catalyst, but will still generally be within the ranges described above. The present invention also relates to a heat-treated shaped mixture for use as a support in catalyst preparation, the shaped mixture having at least 80 wt %, preferably at least 85 wt %, catalyst fines, a total pore volume (TPV) of 0.3 to 0.7 mL / g, more preferably 0.3 to 0.6 mL / g, a macropore volume of 0.005 to 0.15, preferably 0.005 to 0.1 mL / g, more preferably 0.005 to 0.006 mL / g, and a pore volume of 120 to 300 m 2 / g, preferably 145 to 280 m 2 The term "macropore volume >350 Å" refers to the volume of pores having a diameter greater than 350 Å. FIG. 1 shows that the prior art supports have a macropore volume greater than 350 Å of about 0.18 mL / g. The prior art >100 nm macropores are about 0.14 mL / g, while the macropores of support C2 are about 0.09 mL / g and the macropores of support C7 are about 0.05 mL / g.

[0038] The present invention also relates to a process for the hydrotreatment of a hydrocarbon feed, in which the hydrocarbon feed is contacted under hydrotreatment conditions with a catalyst according to the invention, which process according to the invention gives a catalyst which is optionally dried and optionally (pre-)sulfided before being contacted with the hydrocarbon feed. Preferably, the above-mentioned catalyst is used for the hydrotreatment of diesel, naphtha or VGO feeds. [Brief explanation of the drawings]

[0039] [Figure 1] Figure 1 shows the pore size distribution PSD of carrier C7. DETAILED DESCRIPTION OF THE INVENTION

[0040] IV. DETAILED DESCRIPTION OF THE INVENTION The above objects are achieved by providing a process for preparing a hydrotreating catalyst, the process comprising: a) providing a first hydrotreating catalyst comprising a Group VI metal and a Group VIII metal selected from the group consisting of fresh catalyst, regenerated catalyst, rejuvenated catalyst, fresh catalyst fines, regenerated or rejuvenated catalyst fines, or mixtures of the foregoing; b) grinding the hydrotreating catalyst to form catalyst fines, unless the first hydrotreating catalyst already consists of fresh, regenerated, or rejuvenated catalyst fines, or a mixture thereof; c) the mixture comprises at least 60 wt. % catalyst fines, based on the dry weight of the mixture, optionally at least partially combining mixing and grinding, and optionally after grinding during mixing, adding a first hydroprocessing catalyst consisting of fresh catalyst fines, regenerated catalyst fines, or rejuvenated catalyst fines, and mixing the catalyst fines with at least a binder to form a mixture; d) shaping the mixture to form a shaped mixture; e) heat treating the shaped mixture; f) contacting the heat-treated molded mixture with a rejuvenating agent.

[0041] The starting material for the process of the present invention is a first hydrotreating catalyst. The first hydrotreating catalyst comprises a Group VI metal and a Group VIII metal. Group VI metals may include molybdenum, tungsten, and chromium, with molybdenum or tungsten being preferred. Molybdenum is particularly preferred. Group VIII metals include nickel, cobalt, and iron. Nickel, cobalt, or a combination thereof is preferred.

[0042] In hydrotreating catalysts, the content of Group VI and Group VIII metals is generally calculated as their metal oxides. The metal content in the catalyst can be determined by X-ray fluorescence (XRF) or inductively coupled plasma (ICP) spectroscopy. The content is calculated as metal oxide expressed as weight percent of the total dry weight of the catalyst.

[0043] Hydrotreating catalysts typically have a metal content, calculated as oxides, in the range of 0.1 to 50 wt. % based on the total weight of the catalyst. The Group VI metal component is generally present in an amount of 5 to 40 wt. %, preferably 10 to 38 wt. % and more preferably 15 to 35 wt. % calculated as trioxides. The Group VIII metal component is generally present in an amount of 5 to 40 wt. %, preferably 10 to 38 wt. % and more preferably 15 to 35 wt. % calculated as trioxides. Optionally, the catalyst may also contain other components, such as phosphorus, halogens, e.g., fluorine, and boron. In particular, to improve the hydrodenitrogenation activity of the catalyst, 、 The presence of 1-10 wt% phosphorus calculated as P2O5 may be preferred.

[0044] In hydrotreating catalysts, metals are composited with supports. The catalyst supports can include conventional inorganic oxides, such as alumina, silica, silica-alumina, alumina with dispersed silica-alumina, silica-coated alumina, magnesium, zirconia, boron, and titania, as well as mixtures of these oxides. In principle, alumina, silica-alumina, alumina with dispersed silica-alumina, or silica-coated alumina supports are preferred. Alumina and alumina containing up to 10 wt. % silica are particularly preferred. Within this group, transition alumina-containing supports, such as eta-, theta-, and gamma-alumina, are preferred, with gamma-alumina supports being most particularly preferred. In the process of the present invention, the above-mentioned support materials can be used as binders in a mixture with hydrotreating catalyst particles to prepare the catalyst of the present invention.

[0045] Hydrotreating catalysts are conventionally used in hydrotreating processes in the form of spheres, pellets or extrudates, examples of suitable types of extrudates being disclosed in the literature (see, for example, U.S. Pat. No. 4,028,227).

[0046] The starting material can be a fresh hydrotreating catalyst. The term "fresh" refers to a catalyst that has not yet been used in a hydrotreating process. Fresh hydrotreating catalysts can be prepared according to conventional catalyst preparation processes well known to those skilled in the art. Before being used in hydrotreating, the catalyst is generally presulfided to convert the metals to sulfides.

[0047] Fresh hydrotreating catalysts may be prepared according to processes that include additional activation steps, for example, contacting the catalyst with an organic additive and / or an acid.

[0048] The catalyst fines of the fresh first hydrotreating catalyst may be generated during the production, handling, storage, or transportation of the fresh first hydrotreating catalyst prior to use in a hydrotreating process.

[0049] However, the starting material for the process of this invention can also be a spent hydroprocessing catalyst (also called a spent hydroprocessing catalyst) that has been decoked and regenerated. In this case, the catalyst may or may not contain additives prior to its first use. The spent hydroprocessing catalyst may also undergo a further rejuvenation or activation step that involves contacting the regenerated spent catalyst with organic additives and / or acids.

[0050] Regeneration is carried out by contacting the spent hydrotreating catalyst with an oxygen-containing gas under conditions such that the carbon content of the catalyst after regeneration is generally 3 wt% or less, preferably 2 wt% or less, and more preferably 1 wt% or less. After regeneration, the sulfur content of the catalyst is generally less than 2 wt%, preferably less than 1 wt%. Before the regeneration step, the carbon content in the catalyst is generally greater than 5 wt%, generally in the range of 5 to 25 wt%. Before the regeneration step, the sulfur content in the catalyst is generally greater than 5 wt%, generally in the range of 5 to 20 wt%.

[0051] The maximum catalyst temperature during the regeneration step is determined by the characteristics of the catalyst being regenerated and the process constraints, with a higher maximum temperature being preferred in principle because it allows for shorter regeneration times. Longer regeneration times equate to longer residence times of the catalyst material in the regeneration reactor, leading to breakdown of the catalyst material. However, higher regeneration temperatures can result in the formation of large crystallites, risking metal sintering and potentially reducing the metal surface area. Catalysts with higher metal content generally require lower maximum catalyst temperatures than catalysts with lower metal content. Generally, the maximum catalyst temperature during the regeneration process is at most 650°C, preferably at most 575°C, more preferably at most 550°C, and even more preferably at most 525°C.

[0052] The maximum catalyst temperature during the regeneration process is generally at least 300°C, preferably at least 350°C, more preferably at least 400°C, and even more preferably at least 450°C.

[0053] It is noted that all temperatures given herein relate to the temperature of the catalyst unless expressly indicated otherwise, which may be determined by any method known to those skilled in the art, for example, by appropriately positioned thermocouples.

[0054] The regeneration step in the presence of oxygen is preferably carried out in two steps: a first lower temperature step and a second higher temperature step. In the first lower temperature step, the catalyst is contacted with an oxygen-containing gas at a temperature of 100 to 370°C, preferably 175 to 370°C. In the second higher temperature regeneration step, the catalyst is contacted with an oxygen-containing gas at a temperature of 300 to 650°C, preferably 320 to 550°C, and even more preferably 350 to 525°C. The temperature during the second step is preferably at least 10°C, more preferably at least 20°C, higher than the temperature of the first step. The temperature range refers to the set temperature of the oxygen-containing gas. Determining the appropriate temperature range is well within the capabilities of those skilled in the art, given the above guidelines.

[0055] The catalyst is preferably regenerated in a moving bed process, preferably with a bed thickness of 1 to 15 cm, if possible. As used herein, the term "moving bed" is intended to refer to all processes in which the catalyst is moving relative to the equipment, including ebullated bed processes, fluidized bed processes, processes in which the catalyst rotates within the equipment (e.g., Rotorbar), and all other processes in which the catalyst is moving.

[0056] The duration of the regeneration process, including stripping, depends on the properties of the catalyst and the exact manner in which the process is carried out, but is generally between 0.25 and 24 hours, preferably between 0.5 and 16 hours.

[0057] EP1680486 describes a process for activating a hydrotreating catalyst comprising a step of contacting a hydrotreating catalyst comprising a Group VI metal oxide and a Group VIII metal oxide with an acid and an organic additive, wherein the hydrotreating catalyst can be a regenerated spent hydrotreating catalyst or the hydrotreating catalyst can be a fresh hydrotreating catalyst.

[0058] Spent hydrotreating catalysts may have been used once in a hydrotreating process and may have subsequently undergone multiple hydrotreating and regeneration and / or rejuvenation steps. The regeneration process is typically repeated as many times as possible to avoid the need to recycle the catalyst for metal regeneration. However, such regeneration processes can damage the catalyst particles, producing catalyst fines or crushed catalyst particles (extrudates), which can be sieved and used in the process of the present invention. At some point after several regeneration steps, the properties of the regenerated spent catalyst may have deteriorated to the point where it is beneficial to crush it into catalyst fines for use in the process of the present invention. The present invention has the advantage that a very high wt% of catalyst fines can be used and a very high percentage of the original activity can be recovered, thereby avoiding the problems associated with repeated regeneration steps as described above.

[0059] The starting material for the process according to the present invention, i.e., the initial hydrotreating catalyst, can be pulverized to produce catalyst fines. Suitable pulverizers are known to those skilled in the art, and the choice of pulverizer is not critical to the process according to the present invention. Examples of pulverizers suitable for this process include impact mills, ball mills, or jet mills, with impact mills being preferred.

[0060] The starting material contains, or is preferably milled to obtain, particles with a particle size D50 of less than 200 μm, preferably less than 100 μm, more preferably less than 50 μm, even more preferably less than 30 μm, and preferably greater than 1 μm, more preferably greater than 2 μm, even more preferably greater than 4 μm. Small particle sizes are preferred for catalyst fines, considering that they will be bonded together into suitable extrudates. Suitable extrudates meet minimum size, base crush strength, and maximum abrasion requirements, which are typically set by refiners. The particle size distribution is measured using a Malvern particle size distribution analyzer. D50 is the particle size at which the cumulative percentage reaches 50%. D50 is also referred to as the median particle diameter or median particle size.

[0061] D90 is the particle size when the cumulative percentage reaches 90%. In consideration of improved bonding and more stable extrusion, it is preferred that D90 is less than 500 μm, preferably less than 200 μm, more preferably less than 100 μm, and even more preferably less than 80 μm.

[0062] The particle size of the catalyst fines can be achieved by applying the correct settings to the mill used, or sieves can be used. In some cases, the mill has built-in sieves or wind sifters to separate by particle size.

[0063] In the process of the present invention, the first hydrotreating catalyst is optionally crushed to form catalyst fines, which are then mixed with a binder. If the first hydrotreating catalyst consists of catalyst fines, it is not necessary to crush them, but it is generally preferred to also crush the catalyst fines to ensure that the mixture does not contain a significant amount of oversized particles. The shape or form in which the first hydrotreating catalyst is provided by crushing is not critical to the process of the present invention. The catalyst can be provided in full-length extrudate form or in other shapes. The catalyst can also include damaged extrudates or even catalyst fines, the latter of which may not require crushing. The process of the present invention advantageously offers the possibility of using damaged shaped catalyst or catalyst fines that would normally be considered waste material.

[0064] The process for preparing fresh catalyst often produces fresh catalyst fines as an undesirable by-product. Fines can form at any process step where materials are transferred, but are typically formed during the decarboxylation, drying, and shaping processes. Fresh extrudates that do not meet the size and shape requirements can also be used in the process of the present invention. Spent catalyst extrudates can be damaged by mechanical damage during extrudate transportation, mechanical damage during reactor loading and unloading, mechanical attrition of the catalyst, and / or repeated harsh reaction conditions during hydrotreating and / or regeneration, resulting in loss of the desired extrudate length. Spent catalyst fines are also formed under these conditions.

[0065] In a preferred embodiment, the starting material includes damaged extrudates or extrudates that do not meet length specifications, and / or reclaimed spent catalyst fines. These materials cannot be used by refiners regardless of the catalytic activity of the material.

[0066] The catalyst particles are mixed with a binder to form a mixture. The binder can include any material capable of binding the catalyst particles and is typically selected from the group consisting of conventional inorganic oxides, such as alumina, silica, silica-alumina, alumina with dispersed silica-alumina, silica-coated alumina, magnesium, zirconia, boron, and titania, as well as mixtures of these oxides. The binder can also include a precursor of any of these conventional inorganic oxides that can form an inorganic oxide upon heat treatment. For example, boehmite can be used as a binder, which is a precursor to gamma-alumina. The process of the present invention does not necessarily have to replicate the chemical composition of the first hydrotreating catalyst. However, in general, a binder similar to the binder or support in the first hydrotreating catalyst, i.e., a binder also present in the catalyst particles, is preferred to produce a homogeneous mixture and, consequently, a homogeneous extrudate. Furthermore, the purpose of using a binder already present in the catalyst particles is to produce an extrudate with chemical properties similar to those of the first hydrotreating catalyst.

[0067] The mixture contains at least 60 wt% catalyst fines, based on the dry weight of the mixture. According to another preferred embodiment, the mixture contains at least 70 wt%, preferably at least 80 wt%, more preferably at least 85 wt%, even more preferably at least 90 wt%, and most preferably at least 95 wt% catalyst fines, based on the dry weight of the mixture. A high content of catalyst fines in the mixture means that the final catalyst prepared by the process of the present invention has a high content of recycled catalyst material. Furthermore, a high content of catalyst fines in the final catalyst of the present invention means that the final catalyst has a high metal content, since the binder is metal-free. The higher the metal content, the higher the hydrotreating activity.

[0068] In a further aspect, the present invention provides a process for preparing a hydrotreating catalyst, wherein the mixture comprises 100% catalyst fines, based on the dry weight of the mixture, which means that the binder does not comprise dry matter, but may comprise peptizing acid and / or water.

[0069] The binder and catalyst particles form a moldable mixture in the extruder. A suitable extrusion mixture usually requires some moisture. Therefore, the binder usually contains some water. The binder may also contain a pectinizing agent, such as an acid, e.g., nitric acid, citric acid, lactic acid, or acetic acid. The mixture may further contain extrusion aids, such as clay, cellulose, or surfactants, which are usually present in amounts of 5 wt% or less (based on the dry weight of the mixture).

[0070] Prior to molding or extrusion, the moisture content (LOI = loss on ignition) of the mixture can be adjusted as needed. An LOI that is too high can adversely affect the adhesive properties of the material, resulting in weak extrudates that easily break down. An LOI that is too low can result in undesirable extrudates that are weak, too short, cracked, have reduced porosity, or have an uneven surface. Adjusting the moisture content or LOI of the mixture is within the general knowledge of those skilled in the art and can involve simply adding water or acid or controlled evaporation. Determining the appropriate moisture content or LOI for extrusion is within the general knowledge and skill of those skilled in the art. The appropriate LOI for an extrusion mixture is also equipment-specific. As a general rule, the moisture content should be approximately equal to the desired / target total pore volume of the mixture.

[0071] After extrusion, the shaped mixture is heat-treated to dry the catalyst and, in the case of alumina, to change the phase of the binder material in the support, e.g., to gamma, theta, or eta-alumina. The shaped mixture is typically heat-treated at temperatures ranging from 300°C to 900°C, preferably 400°C to 800°C, and more preferably 450°C to 650°C. The heat treatment can be carried out in two steps, e.g., a drying step at 80°C to 150°C and a heat treatment step at the above-mentioned high temperature, or in one step. Drying is preferably carried out to a volatile matter content in the range of 1 to 20 wt% LOI.

[0072] In embodiments according to the invention, when the content of catalyst fines is high and therefore the content of binder is relatively low, it can advantageously be heat treated in one step.

[0073] The heat-treated molding mixture is then contacted with a rejuvenating agent, which may include a complexing agent and an organic additive having a boiling point in the range of 80-500°C and a water solubility of at least 5 grams per liter.

[0074] The result of contact with the rejuvenating agent is indicated by a decrease in the crystalline fraction of the metal in the catalyst, expressed as wt %. Specifically, the decrease in the crystalline fraction in the catalyst is indicated by a decrease in the β-CoMoO4 reflection area at 26.4°2-theta and / or a decrease in the β-NiMoO4 reflection area at 26.58°2-theta relative to Cu-Ka radiation, as measured by X-ray diffraction using a known amount of beta cobalt molybdate as a standard.

[0075] The complexing agent and organic additive are incorporated into the catalyst in liquid form by impregnation. In the case of the complexing agent, this generally means that the complexing agent is in a dissolved state. In the case of the organic additive, whether a solvent is required will depend on its properties. If the organic additive is sufficiently fluid and can penetrate into the pores of the catalyst without the addition of a solvent, the solvent can be omitted. However, a solvent will generally be used. The solvent is typically water, but other compounds such as methanol, ethanol, and other protic solvents may also be suitable, depending on the nature of the additive and / or complexing agent.

[0076] If a solvent is used to incorporate the additive and / or complexing agent into the catalyst, the catalyst can be dried after the impregnation step is complete to remove at least a portion of the solvent, e.g., around 10% (weight percentage relative to the original weight of the compound), thereby producing, for example, a free-flowing powder. In the process according to the present invention, it is important that any drying step is carried out in such a way that at least a portion of the additive and / or complexing agent remains on the catalyst. Thus, the catalyst is not calcined. As a result, the temperature at which a particular additive boils or decomposes will largely determine the drying conditions applied. In the present invention, the drying step should be carried out under conditions such that at least 50%, preferably 70%, and more preferably 90% of the additive incorporated into the catalyst during the impregnation step remains in the catalyst after the drying step. Of course, it is preferable to retain as much additive as possible in the catalyst during the drying step, but for highly volatile compounds, evaporation during the drying step cannot always be avoided. The drying step can be carried out, for example, in air, under vacuum, or in an inert gas. Generally, drying temperatures below 220°C are advantageous, although higher or lower temperatures may be required depending on the nature of the additive. If the impregnation solution comprises water as solvent, drying is preferably carried out at below 150° C., more preferably below 120° C., even more preferably below 100° C., and most preferably below 90° C. After the aging step h), the catalyst is dried in a drying step i).

[0077] The complexing agent and organic additive may be incorporated into the catalyst simultaneously or sequentially in no particular order. For reasons of efficiency, it is preferred that they be incorporated into the catalyst simultaneously.

[0078] The complexing agent is usually an organic acid. In the context of this specification, an organic acid is defined as a compound containing at least one carboxylic acid group (COOH). The organic acid preferably contains at least one carboxyl group and 1 to 20 carbon atoms (carbon atoms in the carboxyl group(s) involved). Within this definition, various groups of complexing agents can be distinguished.

[0079] A first group of currently preferred complexing agents includes acetic acid, citric acid, malic acid, maleic acid, formic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyhexanoic acid, lactic acid, tartaric acid, glyceric acid, gluconic acid, oxalic acid, malonic acid, polyacrylic acid, and ascorbic acid. Within this group, citric acid and lactic acid are preferred. Lactic acid is particularly preferred.

[0080] The second group of complexing agents are nitrogen-containing acids such as EDTA and CyDTA (1,2-cyclohexanediaminetetraacetic acid).

[0081] The organic additives that may be used in combination with the complexing agent in the process according to the invention are organic compounds, i.e., compounds containing at least one carbon atom and at least one hydrogen atom, with a boiling point in the range of 80-500°C and a solubility in water of at least 5 grams per liter at room temperature (20°C) (atmospheric pressure). The additives may be oxygen- or nitrogen-containing compounds.

[0082] The boiling point of the organic additive is preferably in the range of 100 to 400°C, more preferably 150 to 350°C. The boiling point of the additive is balanced based on the desire for the additive to remain on the catalyst during the preparation process, including optional drying and optional aging steps. During use of the catalyst in a hydrotreating or sulfiding process, at least a portion of the additive may be removed from the catalyst. If the organic additive does not have a boiling point but instead decomposes within a specified temperature range, the term boiling point is meant to be synonymous with the decomposition temperature.

[0083] The solubility of the additive is at least 5 grams per liter at room temperature, preferably at least 10 grams per liter. It should be noted that the solubility requirement for the additive is based on two factors. First, compounds that meet this solubility requirement are convenient for application in the impregnation solution. Furthermore, it has been found that compounds that meet these solubility requirements interact with the metal components present in the catalyst to enhance the activity of the final product. Within this definition, various groups of additives can be distinguished.

[0084] The first group of additives includes organic compounds containing at least two oxygen atoms and 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and compounds derived from these compounds. Organic compounds selected from compounds containing at least two oxygen-containing groups, such as carboxyl groups, carbonyl groups, and hydroxyl groups, and compounds derived from these compounds are preferred. Examples of suitable compounds include butanediol, pyruvic aldehyde, glycolaldehyde, and acetaldol.

[0085] Currently, the second group of additives is preferably selected from compounds containing at least two hydroxyl groups and 2 to 10 carbon atoms per molecule, and (poly)ethers of these compounds. Suitable compounds in this group include aliphatic alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolethane, and trimethylolpropane. Ethers of these compounds include diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, and tetrapentylene glycol. This range can be extrapolated to include polyethers such as polyethylene glycol. Other ethers suitable for use in the present invention include ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether. Among these, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, and polyethylene glycols having a molecular weight of 200 to 600 are preferred. Another group of compounds containing at least two hydroxyl groups and 2 to 10 carbon atoms per molecule are sugars. Preferred sugars include monosaccharides, such as glucose and fructose. Ethers thereof include disaccharides, such as lactose, maltose, and saccharose. Polyethers of these compounds include polysaccharides. Organic compounds in this group are preferably substantially saturated, as evidenced by an iodine number of less than 60, preferably less than 20.

[0086] A third group of organic additives suitable for use in the present invention are compounds containing at least one covalently bonded nitrogen atom and at least one carbonyl moiety. Organic compounds of this type preferably contain at least two carbonyl moieties. Preferably, at least one carbonyl moiety is present in a carboxyl group. More preferably, at least one nitrogen atom is covalently bonded to at least two carbon atoms. Preferred organic compounds satisfy formula (I) or (II): (R1R2)N-R3-N(R1'R2') (I) N(R1R2R1') (II) wherein R1, R2, R1', and R2' are each independently selected from alkyl, alkenyl, and aryl, and up to 10 carbon atoms are optionally substituted with one or more groups selected from carbonyl, carboxyl, ester, ether, amino, or amide. R3 is an alkylene group having up to 10 carbon atoms, which may be interrupted by -O- or -NR4-. R4 is selected from the same groups as R1 above. The R3 alkylene group may be substituted with one or more groups selected from carbonyl, carboxyl, ester, ether, amino, or amide. As mentioned above, it is essential that the organic compound of formula (I) or (II) contains at least one carbonyl moiety.

[0087] Preferably, at least two of R1, R2, R1', and R2' in formula (I) and at least two of R1, R2, and R1' in formula (II) have the formula -R5-COOX, where R5 is an alkylene group having 1 to 4 carbon atoms and X is hydrogen or another cation such as ammonium, sodium, potassium, and / or lithium cation. When X is a polyvalent cation, one X may be bonded to more than one -R5-COO group. Typical examples of compounds of formula (I) are ethylenediamine(tetra)acetic acid (EDTA), hydroxyethylenediaminetriacetic acid, and diethylenetriaminepentaacetic acid. Typical examples of compounds of formula (II) are nitrilotriacetic acid (NTA). For solubility reasons, salts of these compounds may be preferred.

[0088] It should be noted that the above discussion of organic additives encompasses a variety of acidic components. When the present specification discusses a combination of an organic acid and an organic additive, it means that (at least) two different compounds are used: one acid and one that meets the solubility and boiling point requirements of the organic additive. The latter compound may or may not be acidic.

[0089] Furthermore, it should be noted that the above description of solvents encompasses a variety of compounds that also fit the description of organic additives. In the context of the present invention, when referring to a combination of a solvent and an organic additive, this means that (at least) two different compounds are used, one of which is the solvent and the other of which meets the solubility and boiling point requirements of the organic additive. The latter compound may or may not be acidic.

[0090] From an environmental point of view, it is preferable to use organic additives that are essentially free of sulfur. Furthermore, sulfur-containing additives are generally not stable to oxygen. Therefore, when using sulfur-containing additives, all subsequent steps must be performed under an inert atmosphere. For this reason, it is also preferable to use additives that do not contain sulfur. This applies to both acids and organic additives. A single compound or a combination of compounds can be used as the organic additive.

[0091] When both a complexing agent and an additive are used, the total amount of the complexing agent and additive used in the process according to the present invention is at least 0.01 moles, preferably at least 0.05 moles, more preferably at least 0.1 moles per mole of the total amount of metals in groups VI and VIII. There is no upper limit to the total amount of the complexing agent and additive added, since an excess amount can be provided without problems. Those skilled in the art can find the optimum amount required to achieve the optimum rejuvenation effect. A suitable molar ratio may be up to 3, preferably up to 2.

[0092] When an organic acid is used as a complexing agent, the amount of the acid is generally 0.01 to 1 mole, preferably 0.05 to 0.5 moles, per mole of the total amount of Group VI and Group VIII metals. The amount of organic acid used is at least 5 wt%, more preferably at least 7 wt%, even more preferably at least 10 wt%, and most preferably at least 15 wt%, based on the catalyst weight. When an organic additive is also used, the organic acid is preferably used at least 5 wt%, more preferably at least 10 wt%, based on the catalyst weight, and the organic additive is used at least 5 wt%, preferably at least 10 wt%, based on the catalyst weight.

[0093] The amount of the organic additive is generally 0.1 to 2.5 moles per mole of the total of the Group VI and Group VIII metals, preferably 0.15 to 1 mole per mole of the total of the Group VI and Group VIII metals, and more preferably 0.2 to 1 mole per mole of the total of the Group VI and Group VIII metals.

[0094] When the rejuvenating agent contains both a complexing agent and an organic additive, the molar ratio of the complexing agent to the additive is generally 0.01-10:1, preferably 0.1-5:1, more preferably 0.15-3:1.

[0095] Generally, if the total amount of rejuvenating agent added is too small, the beneficial effects of rejuvenation will not be obtained. As will be apparent to those skilled in the art, the exact amount of rejuvenating agent to be used in a particular situation will depend on various parameters, including the metal content of the catalyst, the pore volume and pore size distribution of the catalyst, the nature of the rejuvenating agent, the solvent used in the impregnation solution, the impregnation conditions, etc. It is well within the capabilities of those skilled in the art to determine the optimal amount of rejuvenating agent to be used in each particular situation, taking into account the above variables.

[0096] In a preferred embodiment of the process of the present invention, the heat-treated molding mixture is subjected to an aging step after the incorporation of the rejuvenating agent. The aging step is performed while the catalyst is still wet, i.e., before the solvent is removed from the catalyst. The aging time applied in the aging step is a function of temperature. Generally, the aging time decreases with increasing aging temperature. The aging step usually takes at least 15 minutes. After a certain time, e.g., 48 hours or more, no further improvement in activity is observed. When the aging step is performed at a temperature between 0°C and 50°C, the aging time is usually at least 1 hour, and can be at least 2 hours, or at least 6 hours. When the aging step is performed at a temperature above 50°C, the aging time is usually at least 0.5 hours, and can be at least 1 hour, or at least 2 hours. It is also possible to perform the aging step under hydrothermal conditions at temperatures above 100°C for more than 15 minutes. The aging step can also be performed by heating the catalyst with microwaves or induction heating.

[0097] Surprisingly, it has been found that good results (high HDS and HDN activity) can be achieved with relatively short aging times. The commonly used 18-hour aging period does not provide significantly better results than 1-hour aging. Therefore, aging is preferably carried out at a temperature of 20°C to 100°C, preferably 30°C to 80°C, for less than 18 hours, preferably less than 15 hours, less than 10 hours, less than 7 hours, less than 4 hours, or less than 2 hours. In a preferred embodiment, aging is carried out for 0.5 to 2 hours, preferably 0.5 to 1 hour, at 30 to 80°C.

[0098] Preferably, the catalyst composition is aged for a time sufficient to reduce the crystalline fraction to less than 5 wt%, more preferably less than 2.5 wt%. Furthermore, it has been found that in the process according to the invention, the aging time can be significantly reduced and / or better results are obtained if the concentration of complexing agent is at least 5 wt%, preferably at least 7 wt%, and most preferably at least 10 wt% (based on the total weight of the catalyst).

[0099] According to one embodiment of the present invention, the rejuvenated mixture is suitable for transport in its wet state. Drying during transport is not required. Therefore, drying can be performed in situ during the hydrotreating process. However, in practice, it is often preferable to provide a dry catalyst, for example for transport and storage reasons.

[0100] In a further aspect according to the invention, the process further comprises the step of contacting the heat-treated shaped mixture with a solution comprising a Group VI and / or Group VIII metal, which may be carried out before, during, or after contacting the heat-treated shaped mixture with the rejuvenation agent. In a preferred embodiment, the heat-treated shaped mixture is contacted with a solution comprising both a rejuvenation agent and a Group VI and / or Group VIII metal.

[0101] It has been found that good activity can be achieved without the addition of metal in the rejuvenation step when the catalyst contains a high amount of catalyst fines. For example, when the amount of catalyst fines in the catalyst is at least 80%, preferably at least 85%, more preferably at least 90%, and most preferably at least 95%, the HDS activity of such a catalyst (under conditions described in the Examples below) can be at least 50%, preferably at least 55%, more preferably at least 60%, or at least 65% of the HDS activity of fresh commercial KF757 without the addition of metal, and even higher values ​​can be achieved if metal is also added.

[0102] In another aspect of the invention, a Group VI and / or Group VIII metal may be added to the mixture before shaping the mixture. After shaping, the shaped mixture may be subjected to a heat treatment step and / or a rejuvenation step (i.e., contacting the heat-treated shaped mixture with a rejuvenation agent).

[0103] When catalyst particles are mixed with a binder to form a mixture that can be shaped and heat-treated, the metal concentration is diluted. Because activity is related to the amount of metal in the catalyst material, diluting the first-generation hydrotreating catalyst particles with a binder will also reduce the activity of the final hydrotreating catalyst, resulting in a lower activity than would be expected for a fresh catalyst. The objective of the present invention is to restore the activity of the catalyst material as much as possible, preferably achieving at least 60%, more preferably at least 75%, even more preferably at least 85%, and even more preferably at least 90% of the activity of the corresponding fresh hydrotreating catalyst. Therefore, it is advantageous to impregnate the heat-treated shaped mixture with a solution containing a Group VI and / or Group VIII metal.

[0104] The solution may preferably contain metals in amounts and relative proportions that restore the metal content of the first hydrotreating catalyst. In other words, if the mixture contains 80 wt. % catalyst particulates on a dry weight basis, the metal concentration of the shaped, heat-treated mixture will be 80% of the metal concentration in the first hydrotreating catalyst. In a preferred embodiment, the impregnation solution contains metals in amounts such that, after contact with the solution containing Group VI and / or Group VIII metals, the heat-treated shaped mixture contains a metal concentration that is at least 90 wt. %, preferably at least 95 wt. %, and more preferably at least 98 wt. % of the metal concentration in the first hydrotreating catalyst.

[0105] According to another aspect of the invention, the impregnation solution contains metals in an amount such that after contact, the heat-treated shaped mixture contains a metal concentration greater than 100 wt. % of the metal concentration in the first hydrotreating catalyst, which can be advantageous in terms of improved regeneration of catalytic activity.

[0106] According to another aspect of the invention, it is possible to use a Group VI or Group VIII metal in solution that is different from the metal present in the first hydrotreating catalyst, to use only one of the metals, or to use the metals in a different ratio. Variations in the nature or ratio of the metals can affect the activity or selectivity of the final catalyst in the hydrotreating process.

[0107] In another aspect, the present invention relates to a hydrotreating catalyst obtainable by the process according to the invention. This hydrotreating catalyst is characterized by a total pore volume of 0.2 to 1.0 mL / g, preferably 0.3 to 0.6 mL / g. The hydrotreating catalyst typically has a macropore volume of 0.005 to 0.3 mL / g, preferably a macropore volume of less than 0.06 mL / g. In this specification, pores with a diameter greater than 100 nm are considered macropores, and surface areas of 100 to 300 m are considered macropores. 2 / g.

[0108] The hydrotreating catalyst obtained or potentially obtainable by the process of the present invention may be subjected to a drying and sulfiding step before use in the hydrotreating of a hydrocarbon feed, although, as noted above, this is not required. If it is decided to sulfidize the catalyst before use, this can be done by any method known in the art. For example, sulfiding can be achieved by contacting the catalyst with an inorganic or organic sulfur compound, such as hydrogen sulfide, elemental sulfur, or organic polysulfides, or by contacting the catalyst with a hydrocarbon feed to which a sulfur compound has been added. All of this will be known to those skilled in the art as a sulfided catalyst or pre-sulfiding.

[0109] The catalyst of the present invention can be used for the hydrotreating of a wide range of feeds. Any feed containing hydrocarbons is suitable for one or more of the effects of hydrodesulfurization, hydrodenitrogenation, and hydrodearomatization. Examples of suitable feedstocks include petroleum cuts, cuts derived from coal, or hydrocarbons produced from natural gas, optionally in mixtures, or hydrocarbon cuts derived from biomass, including, but not limited to, gasoline, diesel, vacuum diesel, middle distillates, naphtha, atmospheric residue, vacuum residue, atmospheric distillate, vacuum distillate, heavy oil, oil, wax, paraffin, waste oil, debituminized residue, or crude oil, feedstocks obtained from thermal or catalytic conversion processes, lignocellulosic feedstocks, or more generally, feedstocks derived from biomass, organic waste feedstocks, and plant (waste) feedstocks, either alone or in mixtures. The feedstocks to be treated, particularly those mentioned above, generally contain heteroatoms such as sulfur, oxygen, and nitrogen, and, in the case of heavy feedstocks, typically also contain metals. The catalyst is particularly suitable for ultra-deep hydrodesulfurization, i.e., hydrodesulfurization leading to a product sulfur content of less than 200 ppm, especially less than 50 ppm. Conventional process conditions can be applied, such as temperatures in the range of 250°C to 450°C, pressures in the range of 5 to 250 bar, space velocities in the range of 0.1 to 10 h-1, and H2 / oil ratios in the range of 50 to 2000 Nl / l.

[0110] The present invention is further illustrated by the following examples.

[0111] Definitions and Methods The weight db is the dry basis weight after drying at 600°C for 1.5 hours.

[0112] LOI is loss on combustion, weight loss after treatment at 600°C for 1.5 hours.

[0113] CA is citric acid, DEG is diethylene glycol, and LA is lactic acid.

[0114] SA is the surface area measured using nitrogen by the BET method according to ASTM D3663-03 and ASTM D4365-95 on a Micromeritics GEMINI VII Analyzer. Unless otherwise stated, samples are pre-treated by drying at 450°C for 1 hour.

[0115] Particle size distribution (and particle size) is measured by laser light scattering on samples dispersed in water using a Malvern Mastersizer 3000 Hydro LV dispersion unit. D50 is the particle size at which the cumulative percentage in the measured particle size distribution reaches 50%. D50 is also called median particle diameter or median particle size. D90 is the particle size at which the cumulative percentage reaches 90%.

[0116] The pore volume Hg21 (PVHg21) is the pore volume in the pore diameter range of 4.2 to 8000 nm, measured by mercury intrusion porosimetry (AutoPoreIV9520).

[0117] The support is the extruded catalyst support after drying and heat treatment. The final catalyst is the support impregnated with rejuvenating agents and / or metals and optionally dried.

[0118] Side Crushing Strength (SCS) is analyzed on a Vinci SCS tester and performed on 40 particles. The average SCS is determined as force (lbs) per unit length (mm).

[0119] Pore ​​volume water: The pores of a sample of calcined (600°C, 1 hour) particles are filled with water added in a controlled manner. The end point of this titration is indicated by a sudden change in the fluidity of the sample.

[0120] X-ray fluorescence analysis (XRF) is performed using a PANalytical Axios or Zetium. Unless otherwise stated, samples are pre-treated by drying at 450°C for 1 hour.

[0121] XRD measurements were carried out using a Bruker D4 Eneavor XRD instrument.

[0122] Catalyst fines wt% is defined as the weight of catalyst fines (db) relative to the final dry basis weight of the support (db).

[0123] Preparation of catalyst particles A batch of spent commercial hydrotreating catalyst (KF-757) containing cobalt and molybdenum (CoMo) was regenerated by Eurecat SA, France. During the regeneration, only a small amount of dust and short extrudates were sieved off. This fraction of the regenerated catalyst was collected and brought to the laboratory for catalyst preparation. This fraction of the regenerated catalyst was impact milled to obtain catalyst fines with a particle size distribution of D50 = 17.6 μm and 99.8% of the volume being particles with a particle diameter less than 64.6 μm. The catalyst fines contained 4 wt% CoO, 24 wt% MoO, and 2 wt% P2O5 supported on γ-Al2O3.

[0124] Preparation of carrier C1 (80 wt% catalyst fine particles) A three-stage mixing recipe was performed using an Eirich mixer. First, 10,334 g of aqueous HNO3 (1.8% relative to the total water weight) was added to a mixture of 4,393 g of spray-dried alumina and 6,645 g of catalyst fines while mixing at 200 rpm. Next, mixing was continued at 800 rpm until densification was observed, as indicated by a peak in power consumption. 3,629 g of catalyst fines was then added, and mixing continued until densification was again observed, as indicated by a peak in power consumption. In the final step, 3,069 g of catalyst fines was added along with 48 g of modified cellulose extrusion aid (Walocell CMC), and mixing was continued at 600 rpm for 5 minutes. This resulted in a mixture containing 80 wt% catalyst fines based on the dry mixture. This mixture was used for extrusion.

[0125] Extrusion was carried out using a ZSK-32 extruder. The extrudates were dried in a drying chamber at 120°C for a minimum of 3 hours and calcined at 450°C for 1 hour. The resulting extrudates are further referred to herein as carriers. The properties of carrier C1 are shown in Table 1. [Table 1]

[0126] Reference catalyst RC1 A freshly prepared batch of commercial hydrotreating catalyst KF-780 was used as a reference catalyst for hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activity in the hydrotreating process. Reference catalyst RC1 contains 4 wt% CoO, 24 wt% MoO, and 2 wt% P2O5 supported on γ-Al2O3. [Example]

[0127] Examples 1 to 3: Impregnation of support C1 with CA and DEG In each example, the support C1 was impregnated to 95% of the pore volume.

[0128] Example 1: Support C1 was impregnated with an organic solution containing citric acid (CA) and diethylene glycol (DEG) to obtain 5.5 wt% CA and 11 wt% DEG on the final catalyst, based on the dry weight of the final catalyst. The desired amount of solution, 12.60 mL (2.96 g CA (50 wt% aqueous solution) + 3.13 g DEG + 7.42 g water), was poured onto the support (25.66 g dry basis (g db)) with mixing.

[0129] Examples 2-3: The same procedure as in Example 1 was followed, using equal amounts of reagents. The solution (2.39 g CA (50 wt % aqueous solution) + 2.53 DEG + 5.99 g water) was poured onto 20.6 g db support C1 and mixed to provide 5.5 wt % CA and 11 wt % DEG in the final catalyst on a dry basis.

[0130] All impregnated extrudates of Examples 1 to 3 and Examples 4 to 12 described below were aged at 60°C and dried at a product temperature of T=80°C for the times shown in Table 5.

[0131] Examples 4-6: Impregnation of support C1 with CA, DEG, and metals Example 4: Support material C1 was impregnated with a solution containing CA, DEG, Co, Mo, and P metals to achieve a target final composition of 24 wt% MoO, 4 wt% CoO, 2 wt% PO, 5 wt% CA, and 10 wt% DEG, based on the dry weight of the final catalyst. The CoMoP solution was prepared by adding cobalt hydroxide carbonate, molybdenum oxide, and phosphoric acid to water as raw materials. 25.66 g of dry base support material C1 was impregnated with 12.60 ml of a solution consisting of 6.12 g metal sol, 2.96 g CA (50 wt% aqueous solution), 3.13 g DEG, and 3.44 g water. The CA-DEG-CoMoP solution was poured onto the extrudate with stirring.

[0132] Examples 5-6: The same procedure, equivalent amounts, and target final composition were followed as in Example 4. 10.71 mL of solution (4.94 g metal solution + 2.39 g CA (50 wt % aqueous solution) + 2.53 g DEG + 2.78 g water) was poured into 20.58 g of db support C1 with stirring.

[0133] Examples 7-9: Impregnation of LA into carrier C1 Example 7: Support C1 was impregnated with a solution containing lactic acid to obtain a final catalyst with 22 wt% lactic acid. 12.6 mL of the solution (7.96 g lactic acid (88% lactic acid content) + 6.00 g water) was poured onto 25.7 gdb of support C1 while stirring.

[0134] Examples 8-9: The same procedure as in Example 7 was followed, i.e., 10.17 mL of solution (6.43 g lactic acid + 4.84 g water) was poured onto 20.6 g of dry support C1, resulting in 22 wt% lactic acid of the final catalyst weight on a dry weight basis.

[0135] Examples 10-12: Impregnation of LA and metals into support C1 Example 10: Support C1 was impregnated with a solution containing lactic acid and Co, Mo, and P metals. The final target composition was 24 wt% MoO3, 4 wt% CoO, 2 wt% PO5, and 20 wt% lactic acid. The CoMoP solution was prepared using cobalt hydroxide carbonate, molybdenum oxide, and phosphoric acid as raw materials. The raw materials were mixed with water. 25.76 g db (pore volume of water = 0.51 ml / g) of support material C1 was impregnated with 12.60 ml (95% pore volume) of a solution consisting of 6.12 g of metal solution + 7.91 g of lactic acid (88%) + 2.02 g of water. The metal + lactic acid solution was heated until clear and poured onto the extrudates with stirring.

[0136] Examples 11-12: The same procedure and equivalent amounts were followed as in Example 10. 20.7 g of db support C1 was impregnated with 4.94 g of metal solution + 6.43 g of lactic acid (88%) + 1.63 g of water.

[0137] Comparative Example CE1: Impregnation of metal onto support C1 without rejuvenation agent 20.7 gdb of support C1 was impregnated with 10.15 ml (95% pore volume) of a Co, Mo, and P metal solution to achieve a target final composition of 24 wt% MoO3, 4 wt% CoO, and 2 wt% P2O5. The CoMoP solution was prepared by adding the raw materials cobalt hydroxide carbonate, molybdenum oxide, and phosphoric acid to water and heating until a clear solution was obtained. The CoMoP solution was poured onto the extrudates with stirring. The impregnated extrudates were aged as shown in Table 5.

[0138] XRD measurement All XRD measurements were performed using a Bruker D4 Eneavor XRD instrument. The effect of impregnation on the reduction of crystalline phases suggests a redistribution of the active phase. The amount of crystalline β-CoMoO4 present on support C1 and on the impregnated catalysts from Examples 1-12 was quantitatively determined by X-ray diffraction. The crystalline fraction of β-CoMoO4 in a sample (expressed as weight percent) was determined from the X-ray diffraction pattern by evaluating the net peak area of ​​the most intense reflection of beta cobalt molybdate at approximately 26.4°2-theta with Cu-Ka radiation against a standard sample of known amount of beta cobalt molybdate.

[0139] For samples impregnated with CA+DEG (with and without metals), the relative amount of β-CoMoO4 ranged from 2.7 to 3.5 wt%, indicating a decrease in crystalline CoMoO4 after impregnation on support C1 (β-CoMoO4 = 5.6%). For samples impregnated with lactic acid (with 20% metals and without metals), the relative amount of CoMoO4 ranged from 0.7 to 1.8%, indicating a more significant decrease in β-CoMoO4 after impregnation on support C1 (β-CoMoO4 = 5.6%). For all examples, the decrease in the crystalline oxide phase indicates an acceptable redistribution of the active phase. XRD measurements are shown in Table 2. [Table 2]

[0140] Activity measurements of the catalysts of Examples 1 to 12 and the reference catalyst RC1 The catalysts of Examples 1-12 and the reference catalyst RC1 were tested for their hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities under the medium pressure, ultra-low sulfur gas oil conditions shown in Table 3. The samples were tested at equivalent high density loadings, CBD (compacted bulk density) as the respective reference (a commercial fresh CoMo catalyst according to Reference Example 1). [Table 3]

[0141] The diesel fuel feedstock had the properties shown in Table 4. [Table 4]

[0142] The reference catalyst RC1 is set to 100% by definition. All examples are compared and calculated against this reference catalyst. The test results for the catalysts of Examples 1 to 12 and the new reference catalyst RC1 are shown in Table 5. [Table 5]

[0143] Test results (HDS and / or HDN volumetric activity) of the catalyst of the present invention and fresh commercial catalyst RC1 showed that the catalyst rejuvenated with CA+DEG can restore up to 57-85% of the HDS activity of the commercial catalyst, and the catalyst rejuvenated with lactic acid can restore up to 60-90% of the HDS activity of the commercial catalyst. Aging and / or drying does not significantly affect activity. Both LA and CA+DEG can be used as rejuvenating agents.

[0144] Preparation of catalyst fine particles for supports C2 to C6 A batch of commercial hydrotreating catalyst (KF-780) containing cobalt and molybdenum (CoMo) was regenerated and catalyst fines were prepared as described above for support C1, resulting in catalyst fines with a particle size distribution of D50 = 14.1 μm, with 100% of the volume being comprised of particles with a particle diameter less than 64.6 μm. The catalyst fines contained 4.1 wt% CoO, 20.6 wt% MoO, and 2.8 wt% PO supported on γ-AlO.

[0145] Preparation of supports C2-C6 (95 wt% catalyst fine particles) with different binders The mixing recipe was carried out using an Eirich mixer. 137.3 g of binder (spray-dried alumina), 2000 g of catalyst fine particles, and 6 g of extrusion aid were mixed, and 1194 g of aqueous nitric acid solution (0.47% by weight relative to the total weight of water) was added. As a result, a mixture containing 95 wt % catalyst fine particles was obtained based on the dry mixture.

[0146] Extrusion was carried out using a ZSK-32 extruder. The extrudates were dried in a drying chamber at 120°C for a minimum of 3 hours and calcined at 450°C-650°C for 1 hour. The resulting extrudates are further referred to herein as "Carrier C2."

[0147] The pore size distribution (PSD) of support C2 is shown in Figure 1 (cumulative penetration in ml / g of PV by Hg21) and compared with the PSD of support C7 and a prior art support (Example 1) shown in Figure 1 of WO2012021386A1, which was made from 30 wt% catalyst fines and alumina powder. Figure 1 shows that the macropore volume of inventive supports C2 and C7 is much smaller than that of the prior art. That is, the cumulative pore volume of macropores larger than 350 Å is approximately 0.1 ml / g and 0.06 ml / g, respectively, compared to approximately 0.16 ml / g for the prior art. The inventive supports have significantly lower macropore volumes. As shown in Examples 13 and 17, catalysts prepared from support C2 exhibit very high activity, sometimes reaching up to 100% compared to a commercial catalyst (RC2).

[0148] Similarly, supports C3-C6 were prepared with different binders, except that no additional HNO3 was added: silica, aluminum acetate, and Actigel. R A mixed solution of magnesium aluminosilicate or aluminum nitrate binder was used to extrude the catalyst microparticles. The properties of the support are shown in Table 6. [Table 6]

[0149] Reference catalyst RC2 A freshly prepared batch of commercial hydrotreating catalyst KF-780 was used as a reference catalyst for hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activity in the hydrotreating process. Reference catalyst RC2 contains 4.4 wt% CoO, 21 wt% MoO, and 3.2 wt% P2O5 supported on γ-Al2O3.

[0150] Examples 13-16: Carriers C2-C6 impregnated with CA, DEG, Co, Mo, and P Support C2 was impregnated with a solution containing CA, DEG, Co, Mo, and P metals, using organic citric acid (CA) and diethylene glycol (DEG) to achieve a final composition of 21 wt% MoO, 4.4 wt% CoO, and 3.2 wt% P2O5. Based on the dry weight of the final catalyst, the final catalyst was impregnated with 10 wt% CA and 11 wt% DEG. The CoMoP solution was prepared by adding cobalt hydroxide carbonate, molybdenum oxide, and phosphoric acid to water. Similar preparations were performed using supports C3 to C6.

[0151] 103.6 g of support C2 (binder: spray-dried alumina) was impregnated with 50.37 ml of a solution consisting of 3.81 g of metal sol, 0.71 g of H3PO4 (75 wt % aqueous solution), 21.30 g of CA (50 wt % aqueous solution), 11.7 g of DEG, and 20.04 g of water. The CA-DEG-CoMoP solution was poured onto the extrudates with stirring. The impregnated extrudates were aged at 60°C for 45 minutes and then dried at 80°C for 1 hour.

[0152] These catalysts were tested for hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activity under medium pressure ultra-low sulfur gas oil conditions (temperature T=335°C, pressure P=45 bar) as set forth in Tables 3 and 4, and compared with reference catalyst RC2, whose activity is set to 100% by definition. These catalysts were compared to this reference catalyst RC2 in Table 7 below, and the relative activities calculated.

[0153] Example 17: Carrier C2 impregnated with CA, DEG and high content of CoMoP Example 13 was repeated, except that support C2 was impregnated with a higher metal content until the target final composition of 23.5 wt% MoO, 5 wt% CoO, and 5 wt% PO was reached. 103.6 g of db support C2 was impregnated with 17.9 g of a metal solution containing MoO, CoO, and 48 ml of a solution containing 3.33 g HPO (75 wt% aqueous solution), 22 g CA (50 wt% aqueous solution), 12 g DEG, and 6.76 g water. The catalyst was tested as described in Example 13, and the results are shown in Table 7. Example 17 demonstrates that activity can be restored to nearly 100% of that of the fresh commercial catalyst. [Table 7]

[0154] Support C7 (98 wt% catalyst fines) for preparation using aluminum acetate A batch of commercial cobalt and molybdenum (CoMo)-containing hydrotreating catalyst (KF-780) was regenerated and catalyst fines were prepared using the method described above on support C1. The catalyst fines had a particle size distribution of D50 = 13.4 μm, with 100% of the volume being comprised of particles with a particle diameter less than 64.6 μm. The catalyst fines contained 4.1 wt% CoO, 22.5 wt% MoO, and 2.2 wt% PO supported on γ-AlO.

[0155] The mixing recipe was carried out using an Eirich mixer. 127.2 g of aluminum acetate, 2076 g of catalyst fines, and 5.9 g of extrusion aid were mixed with 1058 g of water. This resulted in a mixture containing 98 wt% catalyst fines based on the dry mixture. Extrusion was carried out using a ZSK-32 extruder. The extrudates were dried in a drying chamber at 120 °C for a minimum of 3 hours and calcined at 450 °C to 650 °C for 1 hour. The properties of support C7 are shown in Table 8. The pore size distribution (PSD) of support C7 is shown in Figure 1 (cumulative penetration in ml / g of Hg21).

[0156] Preparation support C8 (80 wt% catalyst fine particles) using alumina and citric acid The catalyst particles on support C8 were prepared by the method described above and had a particle size distribution of D50 = 22.7 μm, with 98.8% of the volume being made up of particles with diameters less than 64.6 μm. The catalyst particles contained 3.9 wt% CoO, 17.7 wt% MoO, and 1.7 wt% PO supported on γ-AlO. The compounding recipe was carried out using an Eirich mixer. 1296 g of aqueous citric acid solution (6.2 wt % based on the total weight of water) was added to a mixture of 549 g of spray-dried alumina, 1727 g of catalyst fines, and 6 g of extrusion aid. This resulted in a mixture containing 80 wt % catalyst fines. Extrusion was carried out using a ZSK-32 extruder. The extrudates were dried in a drying chamber at 120°C for a minimum of 3 hours and calcined at 450°C for 1 hour. The properties of support C8 are shown in Table 8. [Table 8]

Claims

1. 1. A process for preparing a hydrotreating catalyst, the process comprising: a) providing a first hydrotreating catalyst comprising a Group VI metal and a Group VIII metal selected from the group consisting of fresh catalyst, regenerated catalyst, rejuvenated catalyst, fresh catalyst fines, regenerated catalyst fines, or rejuvenated catalyst fines, or mixtures thereof; b) milling the first hydrotreating catalyst to form catalyst fines, unless the first hydrotreating catalyst already consists of fresh catalyst fines, regenerated catalyst fines, rejuvenated catalyst fines, or a mixture thereof; c) said mixture comprising at least 60 wt. % catalyst fines based on said dry weight of said mixture, and optionally at least partially combining said mixing and grinding, and optionally after grinding during mixing, adding a first hydroprocessing catalyst consisting of fresh catalyst fines, regenerated catalyst fines, or rejuvenated catalyst fines, and mixing said catalyst fines with at least a binder to form a mixture; d) shaping the mixture to form a shaped mixture; e) heat treating the shaped mixture; f) contacting said heat-treated molded mixture with a rejuvenating agent.

2. 10. The process of claim 1, further comprising step g) of contacting the heat-treated shaped mixture with a solution comprising a Group VI and / or Group VIII metal and, optionally, a phosphorescent compound, wherein step g) can be performed before, during, or after step f), or wherein the Group VI and / or Group VIII metal is added to the mixture before shaping the mixture.

3. 3. The process according to claim 2, wherein the solution contains Group VI and / or Group VIII metals in an amount such that after contacting the heat-treated shaped mixture contains a metal concentration (wt % of metal oxides) of at least 90 wt %, preferably at least 95 wt %, more preferably at least 98 wt % of the metal concentration in the first hydrotreating catalyst; or the metals are such that the catalyst obtained after step f) contains 5-40 wt %, preferably 10-38 wt %, more preferably 15-35 wt % of Group VI metals, calculated as trioxides, and 1-10 wt % of Group VIII metals, calculated as oxides, preferably 2-8 wt %, and also preferably P ２ O ５ The process wherein the amount of the compound added is such that the compound contains 1 to 10 wt % calculated as the amount of the compound added.

4. 4. The process of claim 2 or 3, wherein step g) of contacting the heat-treated shaped mixture with a solution comprising a Group VI and / or Group VIII metal is carried out during step f) in which the solution comprising a Group VI and / or Group VIII metal also comprises the rejuvenating agent.

5. 10. The process of any preceding claim, wherein the first hydrotreating catalyst comprises a regenerated catalyst obtained by regenerating a spent catalyst.

6. 10. A process according to any preceding claim, wherein the mixture comprises at least 70 wt%, preferably at least 80 wt%, more preferably at least 85 wt%, even more preferably at least 90 wt%, and most preferably at least 95 wt% catalyst fines, based on the dry weight of the mixture.

7. 10. The process according to any preceding claim, wherein the binder comprises one or more selected from the group consisting of inorganic oxides, preferably alumina, silica, silica alumina, magnesia, combinations thereof, salts thereof, and clays, preferably alumina or alumina silica, most preferably gamma alumina, and the binder preferably comprises a material similar to or identical to the binder in the first hydrotreating catalyst.

8. 10. The process of any preceding claim, wherein the catalyst fines have a D50 particle size, or the first hydrotreating catalyst is crushed to form catalyst fines with a D50 particle size of less than 200 μm, preferably less than 100 μm, more preferably less than 50 μm, even more preferably less than 30 μm, and preferably greater than 1 μm, more preferably greater than 2 μm, even more preferably greater than 4 μm; and preferably a D90 of less than 500 μm, preferably less than 200 μm, more preferably less than 100 μm, even more preferably less than 80 μm, and preferably greater than 1 μm, more preferably greater than 2 μm, even more preferably greater than 4 μm.

9. 10. The process of any of the preceding claims, wherein the heat treated shaped mixture comprises at least 80 wt%, preferably at least 85 wt%, of catalyst fines, a total pore volume of 0.3-0.7 mL / g, more preferably 0.3-0.6 mL / g, a macropore volume of more than 350 Å of 0.005-0.15 mL / g, preferably 0.005-0.1 mL / g, more preferably 0.005-0.06 mL / g, a surface area SA of 120-300 m ２ / g, preferably 145 to 280 m ２ / g, and preferably a side crushing strength (SCS) of at least 2 lbs / mm, more preferably at least 3 lbs / mm, and even more preferably at least 4 lbs / mm.

10. 10. A process according to any of the preceding claims, further comprising an ageing step h) after the rejuvenation step f), wherein the ageing is preferably carried out at a temperature between 20°C and 100°C, preferably between 30°C and 80°C, and for a time preferably less than 18 hours, preferably less than 15 hours, 10 hours, 7 hours, 4 hours or less than 2 hours, and more preferably between 0.5 hours and 2 hours, even more preferably between 0.5 hours and 1 hour.

11. 10. A process according to any preceding claim, wherein the rejuvenating agent reduces the crystalline fraction of metal oxides of the heat-treated shaped mixture by preferably at least 20%, preferably at least 30%, or more preferably at least 40%, such that the crystalline fraction of metal oxides is preferably less than 5 wt %, more preferably less than 2.5 wt %.

12. 10. A process according to any of the preceding claims, wherein the rejuvenating agent comprises a complexing agent, preferably consisting of a carboxylic acid containing at least one carboxyl group and 1 to 20 carbon atoms, preferably citric acid or lactic acid, and more preferably in addition to said complexing agent an organic additive, preferably selected from the group of compounds containing at least two hydroxyl groups and 2 to 10 carbon atoms per molecule and said ethers or polyethers of these compounds, preferably wherein the rejuvenating agent is a combination of lactic acid or citric acid and said organic additive.

13. A hydrotreating catalyst obtainable by the process of any one of claims 1 to 12, preferably having a total pore volume of 0.2 to 1.0 mL / g, more preferably 0.3 to 0.7 mL / g, even more preferably 0.3 to 0.6 mL / g, preferably a macropore volume above 100 Å of 0.005 to 0.3 mL / g, more preferably 0.005 to 0.1 mL / g, even more preferably 0.005 to 0.06 mL / g, and a surface area SA of 100 to 300 m ２ / g, and more preferably 120 to 300m ２ / g, more preferably 145 to 280 m ２ / g, and the side crushing strength (SCS) is preferably at least 2 lbs / mm, more preferably at least 3 lbs / mm, and even more preferably at least 4 lbs / mm.

14. 1. A heat-treated shaped mixture for use as a support for said preparation of a hydrotreating catalyst, comprising at least 80 wt %, preferably at least 85 wt %, of catalyst fines, a total pore volume of 0.3 to 0.7 mL / g, more preferably 0.3 to 0.6 mL / g, a macropore volume above 350 Å of 0.005 to 0.15, preferably 0.005 to 0.1 mL / g, more preferably 0.005 to 0.06 mL / g, a surface area SA of 120 to 300 m ２ / g, preferably 145 to 280 m ２ / g, preferably having a lateral crushing strength (SCS) of at least 2 lbs / mm, more preferably at least 3 lbs / mm, and even more preferably at least 4 lbs / mm.

15. 14. A process for hydrotreating a hydrocarbon feed, which hydrocarbon feed is optionally dried and optionally (pre-)sulfided before being contacted under hydrotreating conditions with the catalyst of claim 13 or with a catalyst obtained by the process of any of claims 1 to 12, said hydrocarbon feed being preferably naphtha, VGO type diesel fuel.

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