Hydroprocessing catalysts and related methods

Abstract

A catalyst comprising a porous refractory support at least one active metal taken from the group comprising Ni; Co; Mo and W in catalytically active amount, further comprising V, as well as a method for producing such a catalyst and methods using such a catalyst.

Description

DescriptionTitle of Invention:Hydroprocessing Catalysts and Related Methods Technical Field

[0001] The invention relates to catalysts, methods for their production and the use of such catalysts in hydroprocessing processes.Background Art

[0002] In the field of catalysis, the development of efficient and effective catalysts is crucial for hydroprocessing processes, including hydrodearomatization, hydrodeoxygenation, hydrodenitrogenation, hydrodesulfurization, hydroisomerization and hydrocracking. These processes are essential in the refining of petroleum products, where for example the removal of aromatic compounds and heteroatoms such as nitrogen and sulfur is necessary to meet environmental regulations and improve fuel quality. The activity of catalysts defines the capacity of a plant and the cost of operation, and hence increased catalyst activity is commonly beneficial. Also, in petroleum refining efficient and effective catalysts are crucial in the process of hydrocracking by which large oil molecules are cracked into smaller molecules thereby improving the usefulness and value of the oil. The demand for improved catalytic materials has led to extensive research into the composition and preparation methods of catalysts. The choice of support material, the type and amount of active metals, and the preparation conditions may play significant roles in defining the performance of the catalyst. Porous refractory supports like alumina and silica are commonly used due to their chemical and mechanical stability and high surface area, which can enhance the dispersion of active metals. However, improving the combination of metal composition and processing conditions remains a potential for significant environmental and economical benefits, as it directly impacts the catalyst's activity, selectivity, and longevity. As industries strive for more sustainable and cost-effective solutions, innovations in catalyst design and production continue to be a focal point of research and development.Definitions

[0003] The term catalyst shall mean a material that may be in any form and shape, including but not limited to catalyst pellets and extruded catalyst, comprising a porous carrier, metals and possibly other elements. The term shall include material which contains metals in inactive form, which after appropriate activation such as sulfidation or reduction becomes active.

[0004] Where concentrations of elements are presented in relation to a catalyst, these shall be taken as elemental wt% of the dried material, which may be in inactive oxidic form or active sulfided form, unless the material is specifically stated as “a sulfided catalyst” or “a catalyst precursor in oxidic form”.

[0005] Elements may in the following be referred to by their full name or by their chemical symbol. Unless explicitly specified, no significance shall be implied by either of these terminologies.

[0006] For the purpose of the present application, the unit ppmwt shall designate weight / weight parts per million and %wt shall be understood as weight / weight %.

[0007] Where concentrations in the gas phase are given, they are, unless otherwise specified given as molar concentration.

[0008] Where concentrations in the solid or liquid phase are given, they are, unless otherwise specified given as wt / wt concentration.

[0009] The terminology “at least one element X taken from the group comprising A; B and C” shall be understood as all combinations of A, B and C including a single of these elements up to all of these elements.Summary of Invention

[0010] A catalyst is provided, comprising a porous refractory oxide support and specific weight percentages of one or more of the active metals nickel (Ni), cobalt (Co), molybdenum (Mo), tungsten (W) as well as of an additional novel promoter in the form of vanadium (V). In a specific embodiment the material is characterized by containing 0.05-10 %wt Ni or Co, 1-40 %wt Mo or W, and 0.2- 10 %wt V. The method of obtaining this material involves either providing V as an element in the porous support and contacting the porous support with impregnation liquors containing one or more of Ni, Co, W and Mo or alternativelycontacting the porous support with impregnation liquors containing Ni, Co, W, Mo, and V, and drying or calcining the impregnated support. The catalyst may also be provided by physical mixing of support, promoters and active metals, which subsequently is calcined. Calcining is here defined as heat treating under conditions where the majority of deposited metals, such as at least 80 % of Ni and Co metals, are converted to oxidicform, which requires elevated temperature. Drying occurs at conditions where the conversion to oxidic form isn’t quantitative, especially for Ni and Co, which commonly implies a temperature from 80°C; 120°C; or 150°C to 220°C; 250°C; 300°C; 350°C or 400°C.

[0011] Such catalysts are demonstrated to be more active than similar catalysts according to the prior art. Without being bound by theory, it is assumed that the presence of vanadium in the catalyst may increase the available reactive edge of e.g. molybdenum sulfide clusters, either by enabling a higher dispersion of the active metals, forming smaller clusters or by providing imperfections internally in the clusters.

[0012] As molybdenum sulfide clusters are formed during catalyst activation from molybdenum and other oxide material in the precursor catalyst a high dispersion of the metals oxides is expected to be beneficial for the formation of small molybdenum sulfide clusters. The traditional practice of thermal stabilization of the catalyst at temperatures above 400°C, such as 500°C, may lead to loss of dispersion and for this reason the present invention prefers thermal treatment below 400°C for the catalyst.

[0013] Traditionally the presence of vanadium in hydroprocessing catalysts has been associated with a decrease in catalytic activity. This view seems based on the fact that petroleum contains small amount of vanadium, which as the oil is being catalytically processed may deposit inside the catalyst material leading to reduced activity. However, as identified by the present invention, when vanadium is incorporated into the fresh catalyst material during catalyst manufacture then the presence of vanadium surprisingly shows distinct benefits by increasing catalytic activity.

[0014] The production of catalysts is well documented in textbooks, handbooks, scientific literature, and patents. Essentially the objective is to provide a materialwith a high surface area, and a high dispersion of active metals. Catalysts may be produced in a single step of mixing all components and shaping these by extrusion or pelleting, but more commonly the process is carried out step-wise.

[0015] A first step is commonly production of a support from a high surface refractory material, such as a metal oxide e.g. alumina, silica, silica-alumina, titania, zirconia, magnesia, activated carbon, spinel and molecular sieves or combinations of these materials, or other materials, such as high surface activated carbon. Promoters enhancing the catalytic effect may conveniently be added to the support. Such a material is shaped by pelleting, tableting, granulation or extrusion and is often calcined to provide mechanical stability.

[0016] A second step is commonly impregnation of active metals. This may be carried out in one or multiple steps, in which the desired metals (commonly nickel, cobalt, tungsten and molybdenum) are dissolved to form an impregnation liquor. Promoters enhancing the catalytic effect may also conveniently be added to the impregnation liquor. The composition of the impregnation liquor may also influence the final activity of the catalyst. A common impregnation may be based on stepwise impregnation, e.g. by provision of ammonium heptamolybdate in ammonia solution and nickel nitrate in aqueous solution. From a production perspective, a single impregnation is beneficial, and for this purpose, a wide range of compatible salts and solvents are considered, including nitric acid, phosphoric acid and ammonia-based solutions, to enable maximum solubility in the liquor. This solubility may require prolonged agitation to be complete. For industrial production the viscosity is also an important operational parameter, which is related to the composition of the impregnation liquid. Impregnation is beneficially made by the incipient wetness impregnation method according to which the amount of impregnation liquor is only sufficient for filling the pores of the support, minimizing diffusion effects and metal consumption, and having a minimum of excess liquid outside the catalyst particles.

[0017] In recent years organic additives, such as 2-hydroxyethanoic acid, 2- hydroxypropane-1 ,2,3-tricarboxylic acid, 2-hydroxybutanedioic acid, 2- hydroxypropionic acid, 3-hydroxypropionic acid, 2-, 3- and 4-hydroxybutanoic acids, 1 ,5-pentanedioic acid, 2-, 3-, 4-, 5- and 6-hydroxyhexanoic acids, 2,3- dihydroxybutanedioic acid, 2,3-dihydroxypropanoic acid, 2, 3, 4, 5, 6-pentahydroxyhexanoic acid, poly(2-hydroxypropanoic acid) and (5R)-[(1S)-1,2- dihydroxyethyl]-3,4-dihydroxyfuran-2(5H)-one have been reported in the impregnation liquor. In general acids with a carboxyl group and 6, 4 or fewer carbon atoms are preferred and especially alpha-hydroxy acids. One example is Li et al (J. Phys. Chem. C2022, 126, 18536-18549) who discloses processes for impregnation and identify that impregnation with 2-hydroxybutanedioic acid and calcination in the presence of atmospheric air yields a catalyst with increased activity, and this is believed to be due to increased dispersion of metals over the catalyst surface. In addition to organic acids, it has also been proposed that other organic additives alone or in combination, such as salts (e.g. ammonium salts, nitrates and amines) and oxygenates, such as aldehydes or alcohols, may be added to the impregnation liquor. Commonly the organic additives would have a structure similar to the organic acids mentioned above. The organic additives are commonly of biological origin, and thus the carbon content will be dominated by C14isotopes, and presence on the catalyst surface of C14will be an indicator of such organic additives of biological origin. Analysis by ASTM D6866-16 showing that at least 10%, 20% or 50% of the carbon in a catalyst is C14will be an indication of oxygenates of biological origin being present on the catalyst, with an benefit associated with lower cost.

[0018] In embodiments involving presence of vanadium, vanadyl acetylacetonate in ethanolic solution may be a beneficial impregnation liquor, or vanadium may be provided in aqueous solution of inorganic compounds.

[0019] It is often preferred to impregnate with the minimum volume of impregnation sufficient to completely fill the porosity of the support material; the so-called incipient wetness impregnation.

[0020] The activity of the primary active metals, molybdenum and tungsten, and the primary promoters nickel and cobalt has been demonstrated to sometimes benefit from the presence of additional promoters, such as carbon; phosphorous; boron; fluoride and silicon as well as metals such as platinum; rhodium; iridium and iron. These additional promoters may provide a wide range of benefits, from provision of nano-scale structural stability to playing a chemical role in the catalytic mechanism. Such promotion is reported both from promoters added to the support and from promoters added as part of the impregnation. Thepromoters may be present alone or in combination, and when present in combination the combined presence may have a synergetic effect.

[0021] To fixate metals on the surface of the support and to convert metal salts to metal oxides, the impregnated material is dried and heated at elevated temperature, either in a so-called calcination step, during which the metal salts are converted to oxides at elevated temperature in the presence of oxygen or by drying at lower temperature without oxidation of metal salts.

[0022] A material which comprises a refractory support and dispersed base metals (nickel, cobalt, tungsten and molybdenum), will typically have base metals present in positive oxidation states, possibly as oxides or salts. Such a material is not catalytically active, but well suited for transport from manufacturer to endusers.

[0023] At end-users, but occasionally also at the manufacturer or service companies, the catalyst is sulfided, by contacting it, at elevated temperature such as 300°C, with a gas comprising hydrogen and hydrogen sulfide, optionally in the presence of liquid oil.

[0024] The sulfided material is catalytically active for hydroprocessing processes and robust against presence of sulfur and other elements that otherwise are considered catalyst poisons.

[0025] It is well known that hydrotreatment reactions are catalyzed by molybdenum sulfide or tungsten sulfide clusters, especially when these clusters are promoted by atoms of nickel or cobalt on the cluster surface. The presence of nickel and cobalt in the so-called Ni-Mo-S; Ni-W-S; Co-Mo-S; or Ni-Co-Mo-S structures is believed to ease the formation of catalytically active sites in form of vacancies and / or imperfections. Also, thermodynamic forces favor small metal clusters when nickel or cobalt and molybdenum and tungsten in combination are present. Commonly the atomic Ni:Mo ratio is around 1 :3, such as 1 :2 to 1 :5 for high activity removal of heteroatoms. Monometallic catalysts comprising only Mo-S or W-S will be less active, but may have beneficial selectivity, which may be beneficial in distribution the heat release over a larger reactor volume.Furthermore, it is known to balance this improved selectivity, making a recipe which is not monometallic, but wherein the Ni:Mo ratio is low, such as 1 :6 - 1 :12.While there are specific differences between Ni and Co as well as between Mo and W, the role of Ni and Co (Group VIII metals) are similar and the role of Mo and W (Group VI metals) are similar, and the favorable ratios are also similar. Technical Problem

[0026] While the art of catalyst design and production is well developed, effort to improve catalytic activity remains beneficial, considering a reactor loaded with 1 ton of catalyst may be in operation for several years, treating 25-200 tons of hydrocarbons each day. An increased activity of even a fraction of a percent will therefore represent a massive value to the operator of such a plant and may also be related to improved environmental efficiency of the plant, e.g., due to reduced energy consumption and reduced yield loss. Installation of a more active catalyst will also allow an increase in the volume of treated oil produced in a given plant.Solution to Problem

[0027] We have now identified that promotion of the catalytic activity of Ni-Mo-S clusters occurs when vanadium is present. As the chemical environments for similar sulfided catalysts comprising a Group 6 metal in combination with a Group 9 or Group 10 metal are highly similar, this promotion effect is assumed to be valid for catalysts comprising W and / or Mo as well as Ni and / or Co. Similarly, the effect is assumed to be active for catalysts comprising a support with a content of zeolites and / or silica-alumina, such as hydrocracking and isomerization catalyst.

[0028] The effect of the presence of vanadium upon catalytic activity was evaluated by e.g. Betancourt et al (Fuel Processing Technology 114 (2013) 21-25.) This paper identified improvement of hydrodesulfurization and to a lesser degree hydrodenitrogenation of light cycle oil, but hydrodearomatization was reduced in the presence of vanadium. Similarly, CN110773183 observed a moderate improvement of hydrodemetallization and hydrodesulfurization, but a negative effect on removal of asphaltenes (i.e. hydrodearomatization) in heavy oil.

[0029] We have now identified that a novel catalyst precursor and active catalyst comprising carbon in addition to vanadium, enables a surprising increase in hydrodearomatization activity with increasing amounts of vanadium, which is beneficial not only for hydrodearomatization but also for hydrodenitrogenation,and hydrodesulfurization, and furthermore, we have identified that the effect of vanadium is more pronounced at elevated vanadium concentrations. Our results are based on impregnation in a single step, by use of a liquor comprising 2- hydroxypropane-1 ,2,3-tricarboxylic acid and / or 2-hydroxybutanedioic acid, with subsequent drying at moderate temperature. Without being bound by theory, it is assumed that the effect of the carbon is not a direct chemical effect, but rather that the presence of carbon is an indicator of a beneficial production method, due to the impregnation by such a liquor, possibly in combination with drying of the intermediate catalyst at a temperature between 80 and 400°C.

[0030] The catalyst precursor produced is subsequently sulfided, which results in an active catalyst comprising the chemical elements molybdenum, nickel, vanadium and carbon on an alumina based support. Based on the experience in the field there is however reason to expect that the benefits observed for a Ni-Mo-S composition involving vanadium also are beneficial in terms of catalyst activity for the metal combinations Co-Mo-S, Ni-W-S and Ni-Co-Mo-S, as well as being beneficial for other refractory support materials than alumina.

[0031] The promotion effect of vanadium is also seen for catalysts made from catalysts produced at elevated temperatures, but in this case the effect is less pronounced.

[0032] As mentioned above, the atomic Ni:Mo ratio for conventional catalysts is around 1 :3, such as 1 :2 to 1 :5 for high activity removal of heteroatoms.Monometallic catalysts comprising only Mo-S or W-S will be less active, but may have beneficial selectivity, which may be beneficial in distribution the heat release over a larger reactor volume. Furthermore, it is known to balance this improved selectivity, making a recipe which is not monometallic, but wherein the Ni:Mo ratio is low, such as 1 :6 - 1 :12. When incorporating V into this matrix, the basis of atomic ratios is chosen to be Mo (or W, also from Group VI), with Ni and Co being defined relative to Mo and W, and V similarly defined relative to Mo and W. This makes a common composition of [Mo,W][Ni,Co]aVb where [Mo,W] indicates the sum of Mo and W (on molar basis), [Ni,Co] similarly the sum of Ni and Co (on molar basis) and V the amount (on molar basis) of V. a is the ratio of (Ni+Co):(Mo+W) and b is the ratio of V:(Mo+W). 1 / a is commonly around 1 :3, but may range from 1:1, 1:2 to 1:5, 1:6 or 1:12 depending on application. Similarly,1 / b will commonly be around 1 :3, but may range from 1:1, 1 :2 to 1 :5, 1 :6 or 1 :12 depending on the effect desired. These values are believed to reflect the coordination framework of Mo, which involves 12 associated atoms.

[0033] According to a potential embodiment, the catalyst precursor may be formed by initially contacting a porous refractory oxide support with a single impregnation liquor or stepwise by multiple impregnation liquors. V and possibly also other promoters may be present in the support, be added with impregnation liquor or be provided in both. This will result in the formation of an impregnated support. The impregnation liquors may contain elements such as Mo, W, Ni, Co, and V, which define the catalytic properties of the final material. The impregnated support may then undergo a drying process at a temperature range of 80-400°C, providing a dried impregnated support. It is beneficial that the dried impregnated support is not subjected to oxidizing conditions, such as temperatures above 400°C, which may help in maintaining its properties, including presence of carbon at the catalyst surface and the dispersion of metals on the catalyst.

[0034] To activate the catalyst precursor the dried impregnated support may then be sulfided either in-situ or ex-situ by contacting it with a sulfiding agent, such as H2S, di-methyl-di-sulfide (DMDS) or any other sufficiently reactive sulfur containing compound including fossil or biological feedstock. Sulfided catalyst may in some instances be treated by provision of paraffins or other materials to minimize a risk of self heating. Such a stabilized sulfided catalyst may commonly contain fossil caron from the stabilization and biological carbon from any organic acid used in the impregnation.

[0035] This sulfiding process activates the material for catalytic hydroprocessing applications. In these processes, the hydrocarbon feedstock is contacted with the sulfided catalyst in the presence of hydrogen, under specific pressure and temperature conditions, to achieve the desired conversion. The entire sequence of actions may be designed to optimize the catalytic performance of the material for specific industrial applications, and may be carried out in-situ at the refinery or ex-situ by pre-sulfiding at a dedicated facility. The sulfiding process adds sulfur to the catalyst, by replacing oxygen. Typically the difference in molar mass between sulfur and oxygen reduces the concentration of metals by 10 % - i.e. a metal content of 5 wt% is reduced to 4.5 wt%. In addition, the elevated temperature andpresence of hydrogen will cause carbon to be released as methane, such that carbon may be absent from the sulfided catalyst, or more commonly, the carbon content of the sulfided catalyst may be from 1 % to 50% of the carbon content prior to sulfidation.

[0036] The sulfided catalyst, once produced, and activated may be used in hydrotreatment processes such as hydrodearomatization (HDA), hydrodenitrogenation (HDN), hydrodeoxygenation (HDO) or hydrodesulfurization (HDS) of hydrocarbon compositions, in which the objective is the removal of heteroatoms. These processes involve contacting the hydrocarbon feedstock with the sulfided catalyst in the presence of hydrogen, under specific pressure and temperature conditions, such as presence of hydrogen at a ratio between H2 and oil from 100 Nm3 / m3to 3000 Nm3 / m3(or from 1 to 10 times the theoretical consumption of hydrogen), a pressure of 0.2 MPag; 0.5 MPag or 1 MPag to 10 MPag or 20 MPag and a temperature of 270-400°C. For some highly reactive compounds, e.g. aldehydes and other oxygenates, even moderately elevated temperatures are preferred, in order to minimize a risk of polymerization of the reactive compounds. In this case, significantly lower temperatures are preferred, such as from 80°C, 120°C or 150°C. In this case a catalyst with increased activity may be more beneficial, since this may enable hydrodeoxygenation at temperatures where the risk of polymerization is low. Another observation is that the presence of organic nitrogen may poison the catalyst, and hence a close to complete conversion of organic nitrogen may be a pre-requisite for high activity for other hydrotreatment reactions, which may also make the evaluation of experimental results difficult.

[0037] The process for hydrodearomatization involves contacting the hydrocarbon feedstock with the sulfided catalyst of the present disclosure in the presence of hydrogen, to facilitate the hydrodearomatization of an aromatic hydrocarbon composition by enabling the equilibrium reaction between aromatic hydrocarbons and the corresponding saturated hydrocarbons. This equilibrium shifts towards saturated hydrocarbons at lower temperatures and elevated pressures of hydrogen. Preferred hydrodearomatization conditions involve, presence of hydrogen at a ratio between H2 and oil from 100 Nm3 / m3to 3000 Nm3 / m3(or from 1 to 10 times the theoretical consumption of hydrogen), a pressure of 0.2 MPagor 1 MPag to 10 MPag; 15 MPag or 20 MPag and a temperature of at least 220°C or 270°C and less than 320°C, 350°C or 420°C. When treating e.g. feedstocks to hydrocracking or production of ultralow sulfur diesel (LILSD), active hydrodearomatization is desired in combination with hydrotreatment, to optimize several parameters of the fuel. In this connection hydrodearomatization will be desired at severe and high pressure conditions, such as temperatures above 340°C, 350°C or 360°C, and dependent on services below 370°C, 390°C or 420°C. Increased catalytic activity will enable operation of the catalyst at lower temperatures compared to less active catalysts, and thereby shift the equilibrium between aromatic and non-aromatic compounds towards non-aromatic compounds. The resulting product will, as a consequence of a reduced amount of aromatics, provide a lower density (a.k.a. volume swell, providing a higher volume of product, relative to the number of C-atoms) and a reduced tendency to soot formation.

[0038] The disclosed catalyst is attractive for treating a wide range of feedstocks.Due to the potential for hydrodearomatization, fossil diesel, aromatic heavy fossil oils, including vacuum gas oil and coal derived oils and aromatic feedstocks of renewable origin, such as pyrolysis oils as well as crude tall oil and similar oils comprising aromatics, such as resin and rosin acids may be treated. In addition, fossil and renewable feedstocks in general and especially those with high amounts of heteroatoms will benefit from a material with increased catalytic activity.

[0039] The use of a metal phase with increased activity may also benefit in the case of hydroisomerization and hydrocracking, where the increased activity may be employed to lower the process temperatures, with the benefit of fewer side reactions taking place at these reduced temperatures.Advantageous Effects of Invention

[0040] A first embodiment relates to a hydroprocessing catalyst comprising (i) a porous refractory support; (ii) at least one active metal taken from the group comprising Ni; Co; Mo and W in catalytically active amount, such as Ni in a concentration from 0.05 %wt to 10 %wt, Co in a concentration from 0.05 %wt to 10 %wt, Mo in a concentration from 1 %wt to 40 %wt, or W in a concentrationfrom 1 %wt to 40 %wt, (iii) C in a concentration from 0.1 %wt to 15 %wt and (iv) optionally one of the promoting elements F; P and B in a concentration each from 0.1 %wt to 10 %wt, characterized in the hydroprocessing catalyst further comprising from 0.2 to 10 %wt V, calculated as %wt of elements in the catalyst assuming oxidic state, with the associated benefit of such a catalyst having increased activity in hydroprocessing reactions, notably hydrodearomatization. If the catalyst is in precursor form, sulfur may be absent, present in less than 0.5 wt% from miscellaneous additives or in elevated amounts if the metals are supplied in sulphate form. If the catalyst is in sulfided form, the sulfur content will be elevated, such as from 1 to 30 wt%.

[0041] A second embodiment relates to an aspect of the first embodiment, wherein if Mo or W is present the concentration of each is at least 2 %wt or 3 %wt and less than 15 %wt or 20 %wt, with the associated benefit of providing a less costly and focused range of active Mo and W concentrations.

[0042] A third embodiment relates to an aspect of the second embodiment, wherein if Ni or Co is present the concentration of each is at least 0.2 %wt or 1 %wt and less than 5 %wt; 8 %wt or 10 %wt, with the associated benefit of the presence of Ni or Co increasing the activity of Mo and W, providing a highly active catalyst.

[0043] A fourth embodiment relates to an aspect of any previous embodiment, where the at least one active metal taken from the group comprising Ni; Co; Mo and W consist of Mo only; W only; Ni and Mo; Ni and W; Co and Mo; or Ni, Co and Mo; with the associated benefit of an active catalyst suited well for specific applications, such as selective hydrodeoxygenation (Mo or W alone).

[0044] A fifth embodiment relates to an aspect of any previous embodiment, comprising at least of 0.1 %wt or 1 wt and less than 5 %wt or 10 %wt B, with the associated benefit of increased structural stability, enhanced acidity, and increased metal dispersion.

[0045] A sixth embodiment relates to an aspect of any previous embodiment, comprising at least of 0.3 %wt or 1 wt and less than 5 %wt or 10 %wt P, with the associated benefit of enhanced metal dispersion, increased metal-support interaction, modified acidity, stabilized the catalyst structure, and improved sulfur retention.

[0046] A seventh embodiment relates to an aspect of any previous embodiment, comprising at least of 1 %wt or 2 %wt and less than 5 %wt or 10 %wt C, with the associated benefit of modified surface acidity and hydrophobicity and enhanced metal dispersion.

[0047] An eighth embodiment relates to an aspect of any previous embodiment, comprising at least 0.8 %wt V, 1 %wt or 1.5 %wt V, with the associated benefit of a catalyst having a further increase in activity.

[0048] A ninth embodiment relates to an aspect of any previous embodiment, comprising up to 3.0 %wt V 4.0 %wt V or 5.0 %wt V, with the associated benefit of balancing the cost and complexity of added amounts of vanadium with the increase in activity.

[0049] A tenth embodiment relates to an aspect of any previous embodiment, wherein the porous refractory support comprises at least one compound taken from the group consisting of alumina, silica, silica-alumina, titania, zirconia, magnesia, spinel and molecular sieves, with the associated benefit of alumina and silica support being inexpensive, moderately acidic and stable supports, silica, alumina-silica and molecular sieves having additional acidity which has the effect of supporting reactions breaking carbon-carbon bonds, such as hydrocracking, ring opening and isomerization, and titania, zirconia, magnesia, spinel and molecular sieves being beneficial due to increased stability. The present disclosure may relate to a hydrotreatment catalyst, for which the pore size distribution of the refractory support beneficially involves at least 80% of the pore volume in pores having a radius larger than 5 nm and smaller than 1 pm is found in pores having a radius larger than 10 nm and smaller than 200 nm. This has the associated benefit of such a material being well suited for high activity hydrotreatment. The present disclosure may also relate to a guard type of catalyst, for which the pore size distribution of the refractory support beneficially involves at least 30% of the pore volume in pores having a radius larger than 5 nm and smaller than 1 pm is found in pores having a radius larger than 10 nm and smaller than 200 nm and at least 30% of the pore volume in pores having a radius larger than 5 nm and smaller than 1 pm is found in pores having a radius larger than 200 nm and smaller than 900 nm. This has the associated benefit of such a material being well suited for use as a metal guard. An eleventhembodiment relates to a sulfided hydroprocessing catalyst, comprising i) a porous refractory support; ii) at least one active metal taken from the group comprising Ni, Co, Mo and W in catalytically active amount, such as Ni in a concentration from 0.05 %wt to 10 %wt; Co in a concentration from 0.05 %wt to 10 %wt; Mo in a concentration from 1 %wt to 40 %wt;or W in a concentration from 1 %wt to 40 %wt; iii) C in a concentration each from 0.1 %wt to 8 %wt, 15 %wt or 25 %wt; iv) optionally one of the promoting elements F; P and B in a concentration each from 0.1 %wt to 10 %wt; and v) S in a concentration from 1 to 30 wt%, characterized in the hydroprocessing catalyst further comprisingfrom 0.2 to 10 %wt V, calculated as %wt of elements in the sulfided hydroprocessing catalyst. This has the associated benefit of such a sulfided catalyst being activated for operation by sulfiding at a location separate from the location of producing the catalyst precursor. Due to the nature of sulfidation, the composition of sulfided catalyst may deviate moderately from the composition limits of the catalyst including the combinations with compositions according to other embodiments, but with the exception of the content of C, the deviation will be moderate, due to evaporation of water, release of carbon and replacement of O atoms with S atoms. The mass ratio in sulfided catalyst will for S:Mo in practice be around 0.75, while the ratios S:W, S: Ni and S:Co will be lower.

[0050] A twelfth embodiment relates to a method of producing a hydroprocessing catalyst or a hydroprocessing catalyst precursor involving the steps a) contacting a porous refractory support with one or more impregnation liquors to provide an impregnated support, b) drying the impregnated support at a temperature from 80°C to 400°C, wherein the one or more impregnation liquors in combination comprise V and at least one metal taken from the group comprising Ni; Co; Mo and W, as well as an organic additive, such as an acid, a salt, an alcohol or an aldehyde, preferably containing 3 to 6 carbon atoms, with the associated benefit of providing a catalyst on which the metal is highly dispersed in active clusters, and in which carbon is left on the surface of the hydroprocessing catalyst, and at such low temperatures, the metals of the precipitated salts will typically not be fully converted to oxidic form. This method may provide a hydroprocessing catalyst according to the first to tenth embodiment.

[0051] A thirteenth embodiment relates to an activating the hydroprocessing catalyst precursor of the twelfth embodiment involving the step of sulfiding the hydroprocessing catalyst precursor in-situ or ex-situ by contacting it with hydrogen gas and a reactive sulfur compound such as H2S; DMDS or a sulfur containing composition under active sulfidation conditions, with the associated benefit of converting the catalyst to active sulfide form, and typically active sulfidation conditions will imply a temperature above 250°C.

[0052] A fourteenth embodiment relates to a process for hydroprocessing of a hydrocarbon composition comprising the steps of contacting the hydrocarbon composition with a hydroprocessing catalyst according to one of the first to tenth embodiments, such as a catalyst produced according to the eleventh embodiment in the presence of hydrogen in a partial hydrogen pressure of 0.2-20 MPa and a temperature of 80-400°C.

[0053] A fifteenth embodiment relates to a process for hydrogenation or hydrodearomatization of a hydrocarbon composition comprising 0.5 %wt to 20 wt% olefins or 10 %wt to 70 %wt aromatics comprising the steps of contacting the hydrocarbon composition with a sulfided hydroprocessing catalyst or a catalyst precursor according to one of the first to eleventh embodiments, such as a hydroprocessing catalyst produced according to the twelfth embodiment in the presence of hydrogen, a pressure of 0.2-20 MPa and a temperature of at least 220°C or 270°C and less than 320°C, 350°C or 400°C, with the associated benefit of enabling an active process for saturation of unsaturated carbon-carbon bonds, with potential for a reduced temperature minimizing undesired reactions.

[0054] A fifteenth embodiment relates to a process for hydrotreatment of a hydrocarbon composition comprising one or more heteroatoms taken from the group comprising S; O; N; Cl; F; and Br in a concentration from 10 ppmwt to 50 %wt comprising the step of contacting the hydrocarbon composition with a sulfided hydroprocessing catalyst or a hydroprocessing catalyst precursor according to one of the first to eleventh embodiments, such as a sulfided hydroprocessing catalyst produced according to the twelfth embodiment, with the associated benefit of removing undesired organically bound heteroatoms to a low level, or alternatively at a low temperature, minimizing undesired reactions, and the hydrocarbon composition may be of fossil origin, biological origin or a productof thermochemical decomposition, as well as intermediate products from treatment of such compositions, and the content may vary depending on source and stage of the process, and in fossil feedstock S content may typically be from 100 pprriwt to 10 %wt and N content may typically be from 100 ppmwt to 5 %wt, and in biological feedstock and feedstock originating from thermochemical decomposition S and N will typically be lower, and O may be from 1 %wt to 50 %wt, while halides (Cl, F and Br) typically are below 1 %wt.Brief Description of Drawings

[0055] Fig.1 shows the effect of vanadium concentration in the catalyst on conversion of organically bound nitrogen.

[0056] Fig.2 shows the effect of vanadium concentration in the catalyst presence on conversion of aromatics.

[0057] Fig.3 shows the effect of vanadium concentration in a catalyst on conversion of organically bound nitrogen.

[0058] Fig.4 shows the effect of vanadium concentration in a catalyst on conversion of aromatics.Examples

[0059] Three series of catalysts are evaluated for hydrotreatment. Example 1 describes series I (11 and I2) which comprises vanadium, added by impregnation and example 2 describes series S (S1 and S2) which comprise vanadium added in the support. Reference catalysts I0 and SO are representative of the I and S series, respectively, but contain no vanadium.

[0060] In Example 3 series T (TO and T1) refer to a catalyst with a different impregnation liquid where TO does not comprise vanadium and T1 does comprise vanadium.

[0061] Example 4 shows the effect seen with sulfided catalysts made from catalyst precursor series I and S.

[0062] Example 5 reports experimental results sulfided catalysts from catalyst precursor series T.Example 1

[0063] A catalyst IO absent of vanadium is made as follows: To an alumina support having a BET specific surface area of 191 m2 / g, a pore volume measured by mercury porosimetry of 0.96 mL / g and a mean pore diameter of 7.6 nm defined as the volume median diameter by mercury porosimetry and which is in "extrudate" form, nickel, molybdenum and phosphorous are added by impregnation. The impregnation solution is prepared by dissolving, at 90°C, molybdenum oxide (76.0 g), nickel hydroxide carbonate (27.2 g), 42.2 g of an aqueous solution of phosphoric acid at 85 percent by weight in 75.0 g demineralized water. Following cooling of the liquor to <60°C, 101.4 g of 2- hydroxypropane-1 ,2,3-tricarboxylic acid is added. After incipient wetness impregnation, the alumina extrudates are left to mature in a water-saturated atmosphere for 24 hours at room temperature, the extrudates are dried at 120°C for 16 hours. The final metal composition of the catalyst expressed in the form of oxides and relative to the weight of dry catalyst is then the following: Mo = 11.6 %wt, Ni = 2.7 %wt, P = 2.6 %wt and C = 8.6%.

[0064] A catalyst 11 comprising vanadium is made as follows: To an alumina support having a BET specific surface area of 191 m2 / g, a pore volume measured by mercury porosimetry of 0.96 mL / g and a mean pore diameter of 7.6 nm defined as the volume median diameter by mercury porosimetry and which is in "extrudate" form, nickel, molybdenum, vanadium and phosphorous are added by impregnation. The impregnation solution is prepared by dissolving, at 90°C, molybdenum oxide (38.0 g), nickel hydroxide carbonate (13.6 g) and vanadium pentoxide (1.90 g), 21.1 g of an aqueous solution of phosphoric acid at 85 percent by weight in 37.5 g demineralized water under stirring until dissolved. Following cooling of the liquor to <60°C, 50.7 g of 2-hydroxypropane-1 ,2,3- tricarboxylic acid is added. After incipient wetness impregnation, the alumina extrudates are left to mature in a water-saturated atmosphere for 24 hours at room temperature, and are then dried under nitrogen at 120°C for 16 hours. The final metal composition of the catalyst expressed in the form of oxides and relative to the weight of dry catalyst is then the following: Mo = 11.7 %wt, Ni = 2.7 %wt, V = 0.49 %wt, P = 2.6 %wt and C = 8.0 wt%.

[0065] A catalyst 12 comprising vanadium is made as follows: To an alumina support having a BET specific surface area of 191 m2 / g, a pore volume measured by mercury porosimetry of 0.96 mL / g and a mean pore diameter of 7.6 nm defined as the volume median diameter by mercury porosimetry and which is in "extrudate" form, nickel, molybdenum, vanadium and phosphorous are added by impregnation. The impregnation solution is prepared by dissolving, at 90°C, molybdenum oxide (38.0 g), nickel hydroxide carbonate (13.6 g), vanadium pentoxide (3.80 g), 21.1 g of an aqueous solution of phosphoric acid at 85 percent by weight in 37.5 g demineralized water under stirring until dissolved. Following cooling of the liquor to <60°C, 50.7 g of 2-hydroxypropane-1 ,2,3- tricarboxylic acid is added. After incipient wetness impregnation, the alumina extrudates are left to mature in a water-saturated atmosphere for 24 hours at room temperature, and are then dried under nitrogen at 120°C for 16 hours. The final metal composition of the catalyst expressed in the form of oxides and relative to the weight of dry catalyst is then the following: Mo = 11.6 %wt, Ni = 2.6 %wt, V = 0.98 %wt, P = 2.6 %wt and C = 7.8 wt%.Example 2

[0066] A catalyst S1 comprising vanadium according to the invention is made as follows: To an alumina support containing 3.1 %wt V having a Hg specific surface area of 266 m2 / g, a pore volume measured by mercury porosimetry of 0.877 ml / g and a mean pore diameter of 5.3 nm defined as the volume median diameter by mercury porosimetry and which is in "extrudate" form. Nickel, molybdenum and phosphorous are added by impregnation in similar way to I0. The impregnation solution is prepared by dissolving, at 90°C, molybdenum oxide (76.0 g), nickel hydroxide carbonate (27.2 g), 42.2 g of an aqueous solution of phosphoric acid at 85 percent by weight in 75.0 g demineralized water. Following cooling of the liquor to <60°C, 101.4 g of 2. 2-hydroxypropane-1 ,2,3-tricarboxylic acid is added. After incipient wetness impregnation, the extrudates are dried under nitrogen at 220°C for 2 hours. The final metal composition of the catalyst expressed in the form of oxides and relative to the weight of dry catalyst is: Mo = 14.5 %wt, Ni = 2.7 %wt, V = 1.5 %wt, P = 1.6 %wt and C = 7.5 wt%.

[0067] A catalyst S2 comprising vanadium according to the invention is made as follows: To an alumina support containing 6.2 %wt V having a Hg specific surfacearea of 185 m2 / g, a pore volume measured by mercury porosimetry of 0.872 mL / g and a mean pore diameter of 6.6 nm defined as the volume median diameter by mercury porosimetry and which is in "extrudate" form. Nickel, molybdenum, and phosphorous are added by impregnation in similar way to IO. The impregnation solution is prepared by dissolving, at 90°C, molybdenum oxide (76.0 g), nickel hydroxide carbonate (27.2 g), 42.2 g of an aqueous solution of phosphoric acid at 85 percent by weight in 75.0 g demineralized water. Following cooling of the liquor to <60°C, 101.4 g of 2. 2-hydroxypropane-1 ,2,3-tricarboxylic acid is added. After incipient wetness impregnation, the extrudates are then dried under nitrogen at 220°C for 2 hours. The final metal composition of the catalyst expressed in the form of oxides and relative to the weight of dry catalyst is then the following: Mo = 14.4 %wt, Ni = 2.7 %wt, V = 3.1 %wt, P = 1.7 %wt and C = 7.3 wt%.Example 3

[0068] A catalyst TO not comprising vanadium was made as follows: To an alumina support having a BET specific surface area of 191 m2 / g, a pore volume measured by mercury porosimetry of 0.96 mL / g and a mean pore diameter of 7.6 nm defined as the volume median diameter by mercury porosimetry and which was in "extrudate" form, nickel, molybdenum and phosphorous were added by impregnation. The impregnation solution was prepared by dissolving, at 90°C, molybdenum oxide (44.2 g), nickel hydroxide carbonate (13.3 g) , 12.6 g of an aqueous solution of phosphoric acid at 85 percent by weight in 42.5 g demineralized water under stirring until dissolved. Following cooling of the liquor to <60°C, 21.5 g of 2-hydroxybutanedioic acid was added. After incipient wetness impregnation, the extrudates were then dried under nitrogen at 220°C for 2 h. The final metal composition of the catalyst expressed in the form of oxides and relative to the weight of dry catalyst was then the following: Mo = 17.0 %wt, Ni = 3.2 %wt, V = 0.0 %wt, C = 3.8 wt% and P = 2.0 %wt.

[0069] A catalyst T1 comprising 1.4 wt% vanadium was made as follows: To an alumina support having a BET specific surface area of 191 m2 / g, a pore volume measured by mercury porosimetry of 0.96 mL / g and a mean pore diameter of 7.6 nm defined as the volume median diameter by mercury porosimetry and which was in "extrudate" form, nickel, molybdenum, vanadium and phosphorous wereadded by impregnation. The impregnation solution was prepared by dissolving, at 90°C, molybdenum oxide (44.2 g), nickel hydroxide carbonate (13.3 g) and vanadium pentoxide (4.4 g), 12.6 g of an aqueous solution of phosphoric acid at 85 percent by weight in 42.5 g demineralized water under stirring until dissolved. Following cooling of the liquor to <60°C, 21.5 g of 2-hydroxybutanedioic acid was added. After incipient wetness impregnation, the alumina extrudates were then dried under nitrogen at 220°C for 2 h. The final metal composition of the catalyst expressed in the form of oxides and relative to the weight of dry catalyst was then the following: Mo = 16.5 %wt, Ni = 3.0 %wt, V = 1.4 %wt, C = 3.5 wt% and P = 1.9 %wt.Example 4

[0070] The activity of catalysts IO, 11 and I2 and SO, S1 and S2 is tested with respect to hydrodenitrogenation (HDN) and hydrodearomatization (HDA) of vacuum gas oil (VGO), having the characteristics reported in Table 1.

[0071] The test is performed in an isothermal crossed fixed-bed pilot reactor, the liquid and gaseous flows both in direction from the bottom upward.

[0072] The catalysts, are first sulfided in situ at 350°C in the reactor under pressure by means of the gas oil of the test to which 2 percent by weight of dimethyl disulfide are added.

[0073] The test conditions are a total pressure of 7 MPa, a temperature of 360°C and 364°C, with a hydrogen flow rate of 24 L / h and with a feedstock flow rate of 60 cm3 / h. These conditions are selected such that less than complete conversion would be observed, to enable evaluation of the difference in activity.

[0074] The product exiting the pilot reactor is after removal of its gaseous parts collected as a liquid. This liquid is characterized in terms of aromatic content and content of organically bound nitrogen.

[0075] The saturation of aromatics is similarly indicative of the hydrogenation activity.The conversion of aromatics is only reported for the l-series of catalysts impregnated with vanadium.Example 5

[0076] The activity of catalysts TO and T1 were tested by evaluation of hydrodesulfurization (HDS) and hydrodearomatization (HDA, as indicated by decrease of specific gravity, SG) performance on a mixture of 75 vol% light gas oil (LGO) and 25 vol% light cycle oil (LCO), as characterized in Table 1.

[0077] The test was performed in an isothermal crossed fixed-bed pilot reactor, in which the liquid and gaseous flows both flow downwards..

[0078] The catalysts, were first sulfided in situ at 310°C in the reactor under pressure by means of the gas oil of the test to which 2 percent by weight of dimethyl disulfide are added.

[0079] The test conditions were: a total pressure of 7 MPa, a temperature of 319°C, a LHSV of 1 hr1, and a H2:oil ratio of 400 Nm3 / m3. These conditions resulted in 99.9% HDS conversion, but the difference in activity is still distinctive.

[0080] The product exiting the pilot reactor is after removal of its gaseous parts collected as a liquid. This liquid is characterized in terms of specific gravity and content of organically bound sulfur.

[0081] The specific gravity, corresponds to saturation of aromatics and was indicative of the hydrogenation activity.

[0082] As shown in Fig.3, under conditions resulting in 99.9 % HDS, the remaining amount of sulfur is decreased from 1.18 wt% S to respectively 12 ppmwt with TO and 9 ppmwt with T1 which is a significant increase in effect at 99.9 % HDS, confirming the promoting effect of vanadium.

[0083] For the hydrodearomatization an increase from 27% to 30% in the presence of vanadium was observed, confirming the promoting effect of the presence of vanadium.

[0084] The effect shown in Example 4 for vacuum gas oil, is thus confirmed for the lighter light gas oil / light cycle oil mixtureConclusion

[0085] As shown in Figure 1 and Figure 2, all catalysts are highly efficient, enabling a process converting more than 95% organically bound nitrogen and 15% aromatics. Increasing concentration of vanadium on the catalyst shows increasing conversion of organically bound nitrogen and increasing conversion ofaromatics, both for catalysts impregnated with vanadium and for catalysts in which vanadium is included in the support.

[0086] A comparison of the hydrotreatment activity of the two series of catalysts is not immediately possible, since the temperature of operation differs by 4°C, but for the I series at 364°C the conversion of organically bound nitrogen is 98.0% for 10 and above 99.5% for 11-12, whereas for the S series at 360°C the conversion of organically bound nitrogen is 95.7% for SO and above 96.4% for S1 and S2, which demonstrates that the presence of vanadium increases the catalytic activity both for addition of vanadium by impregnation and via the support. It is also demonstrated that this increased activity is observed at levels of 3 %wt V, without indication of diminishing effect

[0087] For hydrodearomatization, the I series demonstrates a significant increase from 14% to 38%, confirming the promoting effect of the presence of vanadium.

[0088] For the T series an increased hydrodearomatization from 27% to 30% is demonstrated, confirmed the promoting effect of the presence of vanadium.Table 1VGO7255%%LLGCOO / Nitrogen ppmwi1409 284 Sulfur %wt 1.44 1-19 Cloud point °C 40Pour point °C 30Aromatics %wt 44.0 36.5 Monoaromatics %wt 20.5 16.1 Diaromatics %wt 9.4 15.6 Tri+-aromatics %wt 14.2 4.8 Simulated distillationIBP °C 224 98 5wt% °C 316 188 10wt% °C 349 222 30wt% °C 406 271 50wt% °C 439 303 70 wt % °C 476 332 90wt% °C 530 372 95 wt % °C 552 390 FBP °C 595 430

Claims

Claims

1. A hydroprocessing catalyst comprisingi) a porous refractory support;ii) at least one active metal taken from the group comprising Ni, Co, Mo and W in catalytically active amounts, such asNi in a concentration from 0.05 %wt to 10 %wt;Co in a concentration from 0.05 %wt to 10 %wt;Mo in a concentration from 1 %wt to 40 %wt;orW in a concentration from 1 %wt to 40 %wt;iii) C in a concentration from 0.1 %wt to 25 %wt andiv) optionally one of the promoting elements F; P and B in a concentration each from 0.1 %wt to 10 %wt;characterized in the hydroprocessing catalyst further comprising from 0.2 to 10 %wt V, calculated as %wt of elements in the catalyst.

2. A hydroprocessing catalyst according to any claim above, wherein if Mo or W is present, the concentration of each is at least 2 %wt or 3 %wt and less than 15 %wt or 20 %wt.

3. A hydroprocessing catalyst according to claim 2, wherein if Ni or Co is present, the concentration of each is at least 0.2 %wt or 1 %wt and less than 5 %wt, 8 %wt or 10 %wt.

4. A hydroprocessing catalyst according to any claim above, where the at least one active metal taken from the group comprising Ni, Co, Mo and W consist of Mo only; W only; Ni and Mo; Ni and W; Co and Mo; or Ni, Co and Mo.

5. A hydroprocessing catalyst according to any claim above, comprising at least of 0.1 %wt or 1 wt and less than 5 %wt or 10 %wt B.

6. A hydroprocessing catalyst according to any claim above, comprising at least of 0.3 %wt or 1 wt and less than 5 %wt or 10 %wt P.

7. A hydroprocessing catalyst according to any claim above, comprising at least 1 %wt or 2 %wt and less than 5 %wt or 8 %wt, 10 %wt or 25 %wt C.

8. A hydroprocessing catalyst according to any claim above, comprising at least 0.8 %wt, 1 %wt or 1.5 %wt V.

9. A hydroprocessing catalyst according to any claim above, comprising up to 3.0 %wt , 4.0 %wt or 5.0 %wt V.

10. A hydroprocessing catalyst according to any claim above, wherein the porous refractory support comprises at least one compound taken from the group consisting of alumina, silica, silica-alumina, titania, zirconia, magnesia, spinel and molecular sieves.

11. A sulfided hydroprocessing catalyst, comprisingi) a porous refractory support;ii) at least one active metal taken from the group comprising Ni, Co, Mo and W in catalytically active amount, such asNi in a concentration from 0.05 %wt to 10 %wt;Co in a concentration from 0.05 %wt to 10 %wt;Mo in a concentration from 1 %wt to 40 %wt;orW in a concentration from 1 %wt to 40 %wt;iii) C in a concentration each from 0.1 %wt to 8 %wt, 15 %wt or 25 %wt; iv) optionally one of the promoting elements F; P and B in a concentration each from 0.1 %wt to 10 %wt;and v) S in a concentration from 1 to 30 wt%.,characterized in the hydroprocessing catalyst further comprising from 0.2 to 10 %wt V, calculated as %wt of elements in the sulfided hydroprocessing catalyst.

12. A method of producing a hydroprocessing catalyst or a hydroprocessing catalyst precursor involving the stepsa) contacting a porous refractory support with one or more impregnation liquors to provide an impregnated support,b) drying the impregnated support at a temperature from 80°C to 400°C wherein the one or more impregnation liquors in combination comprise V and at least one metal taken from the group comprising Ni; Co; Mo; andW, as well as an organic additive, such as an acid; a salt; or an oxygenate, preferably containing 3 to 6 carbon atoms,.

13. A method of activating a hydroprocessing catalyst precursor produced according to claim 12 involving the step of sulfiding the hydroprocessing catalyst precursor in-situ or ex-situ by contacting it with hydrogen gas and a reactive sulfur compound such as H2S, DMDS or a sulfur containing composition under active sulfidation conditions.

14. A process for hydroprocessing of a hydrocarbon composition comprising the steps of contacting the hydrocarbon composition with a hydroprocessing catalyst according to one of claims 1-10, such as a catalyst produced according to claim 12 in the presence of hydrogen in a partial hydrogen pressure of 0.2-20 MPa and a temperature of 80-400°C.

15. A process for hydrogenation or hydrodearomatization of a hydrocarbon composition comprising 0.5 %wt to 20 %wt olefins or 10 %wt to 70 %wt aromatics comprising the steps of contacting the hydrocarbon composition with a hydroprocessing catalyst according to one of claims 1-10, such as a catalyst produced according to claim 12 in the presence of hydrogen, a pressure of 0.2-20 MPa and a temperature of at least 220°C or 270°C and less than 320°C, 350°C or 400°C.

16. A process for hydrotreatment of a hydrocarbon composition comprising one or more heteroatoms taken from the group comprising S; O; N; Cl; F and Br in a concentration from 10 ppmwt to 50 %wt comprising the step of contacting the hydrocarbon composition with a hydroprocessing catalyst according to one of claims 1-10, such as a catalyst produced according to claim 12 in the presence of hydrogen in a partial hydrogen pressure of 0.2-20 MPa and a temperature of 80°C top 400°C.

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