RU2771815C2 - Hydrotreatment catalyst with titanium-containing carrier and sulfur-containing organic additive - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst, methods for its production and a method for hydrotreatment of hydrocarbon raw materials. The catalyst for hydrotreatment of hydrocarbon raw materials, after its conversion into a sulfidated form, contains: at least one component containing group VIB metal selected from molybdenum and tungsten, at least one component containing group VIII metal selected from nickel and cobalt, at least one component in the form of a sulfur-containing organic additive, selected from a group consisting of thio-lactic acid, mercapto-succinic acid and cysteine, and a component, which is a titanium-containing carrier additionally containing aluminum oxide. At the same time, the amount of titanium component is in the range of 1-60% by wt., expressed as oxide (TiO₂), per the total weight of the catalyst. At least one component in the form of a sulfur-containing organic additive is present in the amount of 1-30% by wt. The method for production of a catalyst intended for subsequent conversion into a sulfidated form for hydrotreatment of hydrocarbon raw materials includes: 1) co-extrusion of a titanium source with porous material containing Al₂O₃ to form an extrudate of the titanium-containing carrier, drying and calcination of the extrudate; or precipitation of the titanium source with an aluminum source, extrusion of the precipitate to form an extrudate of the titanium-containing carrier, drying and calcination of the extrudate; or impregnation of porous material containing Al₂O₃ with the titanium source to form a titanium-containing carrier, drying and calcination of the carrier; 2) impregnation of the calcined extrudate or carrier with the sulfur-containing organic additive selected from a group consisting of thio-lactic acid, mercapto-succinic acid and cysteine with at least one source of group VIB metal selected from molybdenum and tungsten, and at least one source of group VIII metal selected from nickel and cobalt.

EFFECT: when used in the method for the production of TiO₂-containing carriers in combination with certain sulfur-containing organic compounds, highly active hydrotreatment catalysts were obtained.

16 cl, 16 tbl, 58 ex

Description

FIELD OF TECHNOLOGY TO WHICH THE INVENTION RELATES

[0001] The present invention relates to the field of catalysts used for the hydrotreating of hydrocarbon feedstocks in oil refining processes.

SUMMARY OF THE INVENTION

[0002] Hydrotreating catalysts typically consist of a carrier supported by a Group VIB (Periodic Table) metal containing component and a Group VIII (Periodical Table) metal containing component. The most commonly used Group VIB metals are molybdenum and tungsten, while cobalt and nickel are traditional Group VIII metals. Phosphorus may also be present in the catalyst. Prior art methods for preparing these catalysts are characterized in that the support material is mixed with components containing metals for hydrogenation or hydrotreating, for example by impregnation, after which the composite is usually calcined to convert the metals in the components to their oxides. Before being used in hydrotreating, the catalysts are typically sulfided to convert the hydrogenating metals to their sulfides. Methods for activating and regenerating such catalysts are also known.

[0003] It is widely known to use TiO ₂ -containing carriers in hydroprocessing catalysts, which are usually calcined after the application of active metals. It is often reported that the incorporation of TiO ₂ into hydroprocessing carriers results in higher desulfurization activity, but the basis for this behavior is not well understood. For example, US Patent Publications US 20120181219 and US 20130153467 describe a component containing a metal selected from Groups VIA and VIII of the Periodic Table supported on a silicon dioxide-titania-alumina support, with the total area of the diffraction peak corresponding to the crystal structure of the planes ( 101) of anatase titanium dioxide, and the area of the diffraction peak corresponding to the crystal structure of the (110) planes of rutile titanium dioxide is 1/4 or less of the area of the diffraction peak corresponding to the crystal structure of aluminum belonging to the (400) planes of γ-aluminum oxide, in accordance with the data of X-ray diffraction analysis. However, these references do not describe the combination of the present invention (ie, the combination of a TiO ₂ -containing carrier and the use of a sulfur-containing organic additive).

[0004] Another example is US 6,383,975, which describes a catalyst using a support consisting of an alumina matrix having dispersed on its surface or in its mass, or both, a metal oxide from group IVB of the periodic table. The carrier is obtained by coprecipitation, cogelation or impregnation of alumina with a Ti compound soluble in an organic solvent, followed by drying at 100-200°C and calcination at 400-600°C in an oxidizing atmosphere. However, this reference material also does not describe the combination of the present invention, because this material does not reveal the synergistic effect of titanium and sulfur-containing organic additives.

[0005] Another example is US 9463452 describing a catalyst that uses titanium dioxide coated alumina particles formed into extrudates. At the same time, the hydrotreating catalyst contains a metal compound of group 6 of the periodic table, a metal compound of groups 8-10 of the periodic table, a phosphorus compound and a saccharide. The invention of the '452 patent is limited to a very specific production method and the use of only saccharides as possible additives.

[0006] It has been found that when TiO ₂ -containing carriers are used in combination with certain organic sulfur compounds in the preparation process, highly active hydrotreating catalysts can be obtained. The activity of these catalysts is higher than (i) can be achieved on a traditional Al ₂ O ₃ carrier with the same organic compound, or (ii) when TiO ₂ -containing catalysts are prepared without sulfur-containing organic compounds. Moreover, it appears that the activity of the active phase in the catalyst prepared with TiO ₂ -containing supports in combination with sulfur-containing organic compounds is higher than might be expected from the influence of the individual contributions of these constituents. This higher active phase activity can be used to produce higher volumetric activity hydrotreating catalysts or high activity catalysts at significantly lower concentrations of Group VIB and Group VIII metal active components.

[0007] Thus, in one embodiment, the invention provides a catalyst containing at least one component containing a metal of group VIB, at least a component containing a metal of group VIII, from about 1% of the mass. up to about 30% of the mass. C, and preferably from about 1% of the mass. up to about 20% of the mass. C, and more preferably from about 5% of the mass. up to about 15% of the mass. C one or more sulfur-containing organic additives, and a component representing a titanium-containing carrier, while the amount of the titanium component is in the range from about 1% of the mass. up to about 60% wt., preferably from about 3% wt. up to about 60% wt., expressed as oxide (TiO ₂ ) and based on the total weight of the catalyst. The titanium-containing support is obtained by co-extruding or depositing a titanium source with an Al ₂ O ₃ precursor to form a porous support material containing Al ₂ O ₃ , or by impregnating a porous support material containing Al ₂ O ₃ with a titanium source.

[0008] In another embodiment, the invention provides a method for producing a catalyst. The method includes obtaining a Ti-containing porous support material containing Al ₂ O ₃ . This can be achieved by co-extrusion or precipitation of the titanium source with the Al ₂ O ₃ precursor, molding to form support extrudates, followed by drying and calcining. Alternatively, porous Al ₂ O ₃ extrudates can be impregnated with a Ti source, followed by drying and calcining. The Ti-containing porous support is impregnated with a solution containing at least one Group VIB metal source and/or at least one Group VIII metal source. One or more sulfur-containing organic additives are added in the production process, either by co-impregnation with metal sources or by post-impregnation. In this method, the amount of titanium source is sufficient to form a catalyst composition having at least a titanium content in the range of from about 1 wt. up to about 60% wt., preferably from about 3% wt. up to about 60% wt., expressed as oxide (TiO ₂ ) and based on the total weight of the catalyst after calcination.

[0009] In another embodiment, the invention provides a catalyst composition formed as described above. Another embodiment of the invention is a hydrotreating process carried out using a catalyst composition.

[0010] These and other embodiments, advantages, and features of the present invention will become more apparent from the following detailed description, including the appended claims.

DETAILED DESCRIPTION OF THE INVENTION

[0011] Unless otherwise indicated, weight percents (wt. %) used herein are the weight percent of the specified form of substance, based on the total weight of the product for which the specified substance or form of substance is a constituent or component. The weight percent of TiO ₂ and metal oxides of groups VIB and VIII is given relative to the total weight of the final catalyst after calcination, i.e. without the presence of organic compounds and/or water. The mass percentage of organic compounds in the final catalyst is based on the total weight of the final catalyst without calcination. In addition, it should be understood that when describing steps or components or elements that are preferred in any way herein, they are preferred as of the original date of this description, and that such preference(s) may, of course, vary depending specific circumstances or future developments in the field.

[0012] The Group VIB metal component in the catalysts of the invention is selected from the group consisting of molybdenum, tungsten, chromium and a mixture of two or more of the above, with molybdenum and/or tungsten generally being preferred and molybdenum generally being more preferred. The Group VIII metal component is selected from the group consisting of iron, cobalt and nickel, with nickel and/or cobalt generally being preferred. Preferred metal mixtures include a combination of (a) nickel and/or cobalt, and (b) molybdenum and/or tungsten. When the activity of the catalyst in hydrodesulfurization (sometimes hereinafter referred to as "HDS") is important, a combination of cobalt and molybdenum is advantageous and generally preferred. When the activity of the catalyst in hydrodenitrogenation (sometimes hereinafter referred to as "HDN") is important, a combination of nickel and either molybdenum or tungsten is advantageous and generally preferred.

[0013] The Group VIB metal component may be introduced as an oxide, an oxo acid, or an ammonium salt of an oxo or polyoxo anion. Group VIB metal compounds are formally in the +6 oxidation state. Oxides and oxoacids are the preferred group VIB metal compounds. Suitable Group VIB metal compounds in the practice of the present invention include chromium trioxide, chromic acid, ammonium chromate, ammonium dichromate, molybdenum trioxide, molybdic acid, ammonium molybdate, ammonium paramolybdate, tungsten trioxide, tungstic acid, ammonium tungstate, ammonium metatungstate hydrate, ammonium paratungstate, and the like. Preferred Group VIB metal compounds include molybdenum trioxide, molybdic acid, tungstic acid, and tungsten trioxide. Mixtures of any two or more Group VIB metal compounds may be used; a mixture of products will be obtained when compounds having different Group VIB metals are used. The amount of Group VIB metal compound used in the catalyst is typically in the range of about 15% by weight. up to about 30% of the mass. (as trioxide) based on the total weight of the catalyst.

[0014] The Group VIII metal component is typically introduced as an oxide, hydroxide, or salt. Suitable Group VIII metal compounds include, without limitation, cobalt oxide, cobalt hydroxide, cobalt nitrate, cobalt carbonate, cobalt hydroxycarbonate, cobalt acetate, cobalt citrate, nickel oxide, nickel hydroxide, nickel nitrate, nickel carbonate, nickel hydroxycarbonate, nickel acetate, and citrate. nickel. Preferred Group VIII metal compounds include cobalt carbonate, cobalt hydroxycarbonate, cobalt hydroxide, nickel hydroxycarbonate, nickel carbonate and nickel hydroxide. Mixtures of two or more Group VIII metal compounds may be used; when the Group VIII metals of the compounds in the mixture are different, a mixture of products will be obtained. The amount of the Group VIII metal compound used in the catalyst will typically be in the range of about 2 wt. up to about 8% of the mass. (as oxide) based on the total weight of the catalyst. In a preferred embodiment of the invention, the amount of the Group VIII metal compound is in the range of about 2 wt. up to about 6% of the mass. (as oxide) based on the total weight of the catalyst.

[0015] The titanium component is typically introduced as titanium dioxide, titanyl sulfate, titanium sulfate, titanium (IV) bis(ammonium lactate) dihydroxide, titanium alkoxide (e.g., Ti isopropoxide, Ti butoxide, Ti ethoxide, etc.), or TiCl ₄ . The amount of the titanium component in the catalyst will typically be in the range of about 1% wt. up to about 60% wt., preferably from about 3% wt. up to about 60% wt., expressed as oxide (TiO ₂ ) and based on the total weight of the catalyst. In a preferred embodiment of this invention, the amount of the titanium component is in the range from about 5 wt%. up to about 50% wt., expressed as oxide (TiO ₂ ) and based on the total weight of the catalyst.

[0016] The catalyst support may also contain conventional oxides, such as alumina, silica, silica-alumina, silica-alumina dispersed alumina, silica-coated alumina, alumina-coated silica. In general, preference is given to a carrier of alumina, silica-alumina, alumina with silica-alumina dispersed therein, alumina-coated silica or silica-coated alumina. Particular preference is given to alumina and alumina containing up to 5% of the mass. silicon dioxide. The silicon component used in the preparation of the carrier is usually sodium silicate (water glass) or silicon dioxide. Combining the silicon source with the alumina source can be done, for example, by co-precipitation, kneading (co-extrusion), immersion, impregnation, etc. Preferably, the silicon source is introduced during the deposition step. For inclusion, the silicon compound can also be dispersed in a solvent if desired. A transition alumina-containing support, such as eta-, theta- or gamma-alumina, is preferred in this group, with gamma-alumina being most preferred.

[0017] The physical properties of the final carrier are not critical to the method of the invention, since a synergistic effect should always be observed between the use of titanium-containing carriers and sulfur-containing organic compounds. However, it is known that there is a range of pore sizes, surface area and pore volume that works best depending on the hydroprocessing employed. All physical properties are measured using nitrogen physical adsorption methods (Quadrasorb equipment and pre-treatment at 300°C overnight under vacuum).

[0018] The pore volume of the carrier (measured at 100 nm, taking into account the De Boer and Kelvin equations for converting relative pressure to pore diameter) will typically be in the range of 0.2-2 ml/g, preferably 0.4-1 ml/ G. The specific surface area of the carrier is usually in the range of 50-400 m ² /g (measured by the BET method). Preferably the support will have an average pore diameter in the range of 5-15 nm.

[0019] Typically, the catalyst is used, for example, in the form of spheres or extrudates. Examples of suitable types of extrudates are described in the literature (see, for example, US patent No. 4028227).

[0020] The titanium compound can be incorporated into the carrier by impregnation, co-extrusion or deposition, atomic layer deposition (ALD) or chemical vapor deposition (CVD). Preferably, the titanium component is deposited along with the other carrier components since it is believed, without being bound by theory, that precipitation results in a better dispersion of the titanium component used in the high activity catalyst of this invention than can be achieved by co-extrusion. In addition, the addition of the titanium component at this stage prevents the need for an additional processing step, as is the case with impregnation, ALD or CVD.

[0021] When titanium is added by co-precipitation, known co-precipitation methods can be used. In particular, aluminum sulfate (Alum) and titanyl sulfate (TiOSO ₄ ) or titanium sulfate can be mixed in one stream, and sodium aluminate (Natal) is dosed either simultaneously or sequentially into a volume of water at elevated T and pH > 7. Composition and volume the flow rate of Natal and Alum/TiOSO ₄ /titanium sulfate can be adjusted to achieve the desired final content of TiO ₂ in thus created TiO ₂ /Al ₂ O ₃ material. The pH value can be constantly monitored with NaOH or H ₂ SO ₄ . The total dosing time can vary from 10 minutes to 2 hours, and the final concentration of solids in the reactor will be approximately 2-10% by weight. In the next step, the pH can be raised with NaOH or Natal to 9-12 for aging. The suspension is then filtered and washed. The resulting solid may then be formed into molded articles by extrusion, granulation, or compression, which may be preceded by drying, spray drying, milling, kneading, and other methods known in the art to produce an extrudable material.

[0022] "Shock" precipitation (strike precipitation) is very similar to the processes of co-precipitation, however, the acid stream is added to the main components dispersed in the reaction vessel. Natal is diluted in water and liquid glass is added with vigorous stirring while heating at 60°C. Aluminum sulfate and titanyl sulfate are added to this mixture over 20 minutes with a final pH of 6.5. During the addition, the pH is not adjusted, which allows precipitation at full dosing of both streams. NaOH is used to adjust the pH to 7.2 and the mixture is kept for 1 hour at 60° C. with stirring. The filter cake is resuspended with water, adjusted to pH 10 with ammonia and kept at 95° C. for 1 hour with stirring. The suspension is then filtered and washed with water to remove excess ammonia. The resulting solid may then be formed into molded articles by extrusion, granulation, or compression, which may be preceded by drying, spray drying, milling, kneading, and other methods known in the art to produce an extrudable material.

[0023] The precipitation step may be carried out by reacting or precipitating a Ti precursor such as titanyl sulfate in a suspension of boehmite or pseudoboehmite in water. First, aluminum oxide is precipitated by simultaneously dosing sodium aluminate (Natal) and aluminum sulfate (Alum) into a volume of water at elevated T and pH>7. The Natal and Alum fluxes can be adjusted and the pH adjusted with NaOH or H ₂ SO ₄ . After keeping at pH 9-12, filtering and washing, the boehmite or pseudoboehmite filter cake thus obtained is resuspended in water. To this slurry, TiOSO ₄ or titanium sulfate can be added, either simultaneously or sequentially with NaOH, at elevated T and pH>7 over a period of about 10 minutes to 1 hour. The slurry is then filtered and washed. The solid thus obtained may then be formed into molded articles by extrusion, granulation or compression, which may be preceded by drying, spray drying, milling, kneading and other methods known in the art to obtain an extrudable material.

[0024] Co-extrusion is carried out by adding the titanium component to the alumina precursor component during the kneading or kneading step. The moment of adding is not fixed. The titanium component is added as a solid or as a solution. During the kneading or mixing step, the mixture is heated to the desired temperature to remove any excess solvent/water, if necessary. The kneading or mixing is completed when the desired moisture content (determined by loss on ignition at a temperature in the range of 500-600° C.) is reached. The mixture is then molded into extrudates by a suitable molding process. In addition to extrusion, molding can be carried out by granulation or compression.

[0025] The supports obtained by precipitation and co-extrusion processes are then dried at a temperature in the range of 80-200°C to remove a significant amount of solvent/water and are further calcined in air or under inert conditions with or without steam at a temperature in the range of 400 -900°C, resulting in alumina, in a carrier containing a transitional alumina, for example gamma, theta or eta alumina. The titanium dioxide component will also be present as an oxide, such as anatase or rutile. The calcination can be carried out in a static mode or a rotational mode.

[0026] When adding titanium by impregnation, the titanium precursor is applied to a porous support containing Al ₂ O ₃ . Known impregnation methods may be used. In particular, impregnation with filling of the pore volume is preferred. A solution of an aqueous titanium dioxide precursor such as titanyl sulfate, titanium sulfate or titanium (IV) bis(ammonium lactate) dihydroxide is prepared. Alternatively, a non-aqueous solution of titanium alkoxide can be prepared. The alumina extrudate is then coated/impregnated with a titanium solution. The impregnated carrier thus formed is then dried at a temperature in the range of 80-200°C to remove a significant amount of solvent/water and is then typically calcined in air or under inert conditions with or without steam at a temperature in the range of 400-700°C.

[0027] When preparing a support material containing TiO ₂ , it may be preferable that one part of TiO ₂ is introduced in one stage, while another part of TiO ₂ is introduced in another stage.

[0028] The calcined extrudates containing Al ₂ O ₃ and TiO ₂ are then impregnated with a solution containing a Group VIB metal source and/or a Group VIII metal source and optionally a phosphorus source. The impregnation is carried out by impregnation by pore volume with an impregnating solution which may also contain selected organic sulfur additives in a suitable solvent. The solvent used in the preparation of the impregnation solution of the additive is typically water, although other components such as methanol, ethanol and other alcohols may also be suitable. The impregnation can be carried out at room temperature or at elevated temperatures, but is usually carried out at a temperature of about 20-100°C. Instead of impregnation methods, immersion methods, spray methods, etc. can be used. After impregnation, an optional drying step is carried out to remove water, but leaving (most of) the organic additive on the catalyst. Drying is usually carried out at a temperature in the range of 25-220° C., although higher T, drying with a short contact time can also be used. In the case where sulfur-containing organic compounds are not added to the impregnation solution containing precursor metals, a subsequent impregnation step is carried out.

[0029] The final catalyst also contains one or more organic sulfur additives. One or more sulfur-containing organic additive is added in an amount of from about 1% of the mass. up to about 30% of the mass. C, and preferably from about 1% of the mass. up to about 20% of the mass. C, and more preferably from about 5% of the mass. up to about 15% of the mass. C by weight of the final catalyst. This organic additive may be added together with the Group VIB metal source and/or the Group VIII metal source, or in a separate step. The sulfur-containing organic compound is preferably selected from the group of compounds comprising a mercaptocarboxylic acid of the formula HS-R-COOH, where R is a straight or branched, and saturated or unsaturated carbon backbone (C ₁ -C ₁₁ with or without heteroatoms such as nitrogen ) with an optional nitrogen-containing functional group such as amine, amide, etc. Suitable examples of such mercaptocarboxylic acid include, without limitation, thioglycolic acid, thiolactic acid, thiopropionic acid, mercaptosuccinic acid, and cysteine, or mixtures thereof.

[0030] Metals, additional phosphorus and sulfur-containing organic additives can be introduced into the extrudates in one or more stages. The solutions used may or may not be heated.

[0031] For a one-step approach, a solution is prepared containing at least one source of a Group VIB metal, at least one source of a Group VIII metal, together with a source of phosphorus in varying ratios, typically using water as solvent. Other carboxylic acids may be added, such as citric acid, malonic acid, gluconic acid, adipic acid and malic acid. The resulting solution may be acidic and may have a pH in the range of 0-7. Additional mercaptocarboxylic acid may also be added in a subsequent step. Said solution, either heated or as such, is injected onto the carrier extrudates over a period of 2-60 minutes (depending on the total amount and metal content of the catalyst), remaining close to, but not necessarily reaching, saturation of their pore volume. After impregnation, the catalyst is kept to obtain free-flowing extrudates and additionally kept at a temperature of 60-160°C, preferably 80-120°C. If higher amounts of additives are used, corresponding to an additive/metal ratio greater than about 0.5 equivalent of the amount of sulfur required to form MoS ₂ , WS ₂ , CoS and/or NiS, the resulting solution may be too viscous for impregnation. In addition, precipitation of metals/additives should be avoided. In the case of precipitation, it is not recommended to filter the precipitate to obtain a solution suitable for impregnation and subsequently impregnate with this filtered solution. Viscous or precipitated solutions should be avoided by various methods known in the art. One approach would be to further dilute with water (or other suitable solvent), possibly reaching volumes well in excess of the carrier's existing pore volume. In such a case, the solution may be added in two or more steps, with intermediate drying steps. Heating the solution is another common method, although excessive heating in air can result in an even more viscous solution. In this regard, cooling or working with a solution in an inert atmosphere is considered an acceptable approach. The final prepared catalyst is ultimately subjected to a final holding step at a temperature of 60-160°C, preferably 80-120°C. Aging is usually carried out in air. Optionally, keeping the catalysts in an inert atmosphere can be beneficial to improve physical properties (eg, to prevent lumping between extrudates), but is not critical to the invention. Prior to activation (pre-sulfiding) and catalytic testing, calcination treatment at temperatures above the activation and testing temperature, especially if it leads to oxidation of the sulfur-containing component, is not preferred because it may reduce catalytic activity. In addition, any other treatment that oxidizes the sulfur component should be avoided.

[0032] In a multi-step approach, the metals are first introduced into the carrier, and then the mercaptocarboxylic acid additive is added. The metal-containing solution may or may not be heated. The carrier extrudates are impregnated with a solution containing at least one Group VIB metal source, at least one Group VIII metal source together with a source of phosphorus in varying proportions. Other carboxylic acids may be added, such as citric acid and the above acids, either as part of the metal solution or in subsequent steps. Water is usually used as the solvent for preparing the impregnating solution, although it is believed that other solvents known in the art may be used. The resulting solution may be acidic and have a pH in the range of 0-7. The specified solution is injected into the extrudates, using 90-120% saturation of the pores. During the mixing/impregnation process, the catalyst is held in rotation to ensure uniform mixing of all components. The impregnated material is then dried at a temperature of 80-150° C., preferably 100-120° C., until excess water is removed and "free-flowing" catalyst extrudates are obtained. The resulting catalyst may have a moisture content in the range of 0-20%. Optionally, the impregnated extrudates can be calcined at temperatures up to (eg) 600°C. The mercaptocarboxylic acid is then carefully added as drops or a continuous stream to the resulting catalysts (as a pure liquid or as a mixture with water or other suitable solvent) over a period of time, typically 2-60 minutes, depending on the total amount of catalyst and content in him metals. The impregnated catalyst is held until free-flowing extrudates are obtained. The catalyst is then subjected to a final holding/heat treatment step (in air or in an inert atmosphere) at a temperature of 60-160°C, preferably 80-120°C. Aging is usually carried out in air. Optionally, keeping the catalysts in an inert atmosphere can be beneficial to improve physical properties (eg, to prevent lumping between extrudates), but is not critical to the invention. Prior to activation (pre-sulfiding) and catalytic testing, calcination treatment at temperatures above the activation and testing temperature, especially if it leads to oxidation of the sulfur-containing component, is not preferred because it may reduce catalytic activity. In addition, any other treatment that oxidizes the sulfur component should be avoided.

[0033] In the practice of this invention, the impregnation solution may optionally include a phosphorus component. The phosphorus component is a compound that is usually a water-soluble acidic phosphorus compound, in particular an oxygen-containing inorganic phosphorus-containing acid. Examples of suitable phosphorus compounds include metaphosphoric acid, pyrophosphoric acid, phosphorous acid, orthophosphoric acid, triphosphoric acid, tetraphosphoric acid, and phosphoric acid precursors such as ammonium hydrogen phosphates (monoammonium dihydrogenphosphate, diammonium monohydrogenphosphate, triammonium phosphate). Mixtures of two or more phosphorus compounds may be used. The phosphorus compound may be used in liquid or solid form. The preferred phosphorus compound is phosphoric acid (H ₃ PO ₄ ) or ammonium hydrogen phosphate, preferably in aqueous solution. The amount of phosphorus compound used in the catalyst is preferably at least about 1 wt%. (in the form of oxide P ₂ O ₅ ) based on the total weight of the catalyst and more preferably in the range from about 1 wt%. up to about 8% of the mass. (in the form of oxide P ₂ O ₅ ) based on the total weight of the catalyst.

[0034] Optionally, the catalysts of the invention may be subjected to a sulfidation (treatment) step to convert the metal components to their sulfides. As used herein, the terms "sulfiding step" and "sulfiding step" mean any process step in which a sulfur-containing compound is added to a catalyst composition and in which at least a portion of the hydrogenating metal components present in the catalyst is converted to the sulfide form, either directly , or after activating treatment with hydrogen. Suitable sulfidation processes are known in the art. The sulfidation step can take place ex situ in relation to the reactor in which the catalyst is to be used for the hydrotreating of the hydrocarbon feedstock, in situ, or a combination of ex situ and in situ in relation to the reactor.

[0035] The ex situ sulfiding processes take place outside of the reactor in which the catalyst is to be used to hydrotreat the hydrocarbon feed. In such a process, the catalyst is brought into contact with a sulfur compound, such as polysulfide or elemental sulphur, outside the reactor and, if necessary, dried. In the second step, the material is treated with hydrogen gas at elevated temperature in a reactor, optionally in the presence of a feedstock, to activate the catalyst, i. bringing the catalyst into a sulfided state.

[0036] In situ sulfiding processes take place in a reactor in which a catalyst is to be used to hydrotreat hydrocarbon feeds. In this case, the catalyst is contacted in a reactor at elevated temperature with a stream of hydrogen gas mixed with a sulfiding agent such as hydrogen sulfide or a compound which, under prevailing conditions, can decompose to form hydrogen sulfide. It is also possible to use a hydrogen gas stream combined with a hydrocarbon feed containing a sulfur compound which, under prevailing conditions, can decompose to form hydrogen sulfide. In the latter case, the catalyst can be sulfided by contacting a hydrocarbon feed containing an added sulfiding agent (enriched hydrocarbon feed), and it is also possible to use a sulfur-containing hydrocarbon feed without any added sulfiding agent, since the sulfur components present in the feed will be converted to hydrogen sulfide. in the presence of a catalyst. Combinations of different sulfiding techniques can also be used. The use of enriched hydrocarbon feedstock may be preferred.

[0037] In addition to the activity gain from using these mercaptocarboxylic acids, the use of mercaptocarboxylic acids is advantageous due to the sulfiding properties of the final catalyst: due to the presence of sulfur in the compound, sulfiding of the catalyst is (in part) achieved by sulfur from the catalyst itself. This opens up opportunities for DMDS-lean (or feed-only) runs or even hydrogen-only runs. As used herein, the expressions "sulfiding step" and/or "sulfiding step" and/or "activation step" means any process step in which at least a portion (or all) of the hydrogenating metal components present in the catalyst are converted to the (active) sulfide form, usually after an activating treatment with hydrogen and optionally with the additional presence of a feedstock and/or a (sulphur-rich) enriching agent. Suitable sulfidation or activation processes are known in the art. The sulfidation step can take place ex situ in relation to the reactor in which the catalyst is to be used in the hydrotreating of the hydrocarbon feedstock, in situ, or a combination of ex situ and in situ in relation to the reactor.

[0038] Regardless of the approach (ex situ vs. in situ), the catalysts described in this invention can be activated using conventional start-up methods known in the art. Typically, the catalyst is contacted in a reactor at an elevated temperature with a stream of hydrogen gas mixed with a sulfiding agent such as hydrogen sulfide or a compound which, under prevailing conditions, can decompose to form hydrogen sulfide. It is also possible to use a sulfur containing hydrocarbon feed without any added sulfiding agent, since the sulfur components present in the feed will be converted to hydrogen sulfide in the presence of a catalyst.

[0039] the Catalyst compositions of this invention are compositions obtained by the above method, regardless of whether this method includes an optional step of sulfiding.

[0040] The resulting catalyst product of the present invention is suitable for use in the hydrotreating, hydrodenitrogenation and/or hydrodesulfurization (also collectively referred to herein as "hydrotreating") of hydrocarbon feedstock in contact with a catalyst under hydrotreating conditions. Such hydrotreating conditions are temperatures in the range of 250-450°C, pressures in the range of 5-250 bar (0.5-25 MPa), liquid space velocities in the range of 0.1-10 l/h and hydrogen/oil ratios in the range of 50 -2000 n.l/l. Examples of suitable hydrocarbon feedstocks to be treated in this manner vary widely and include middle distillates, kerosene, naphtha, vacuum gas oils, heavy gas oils, and the like.

[0041] The following describes the experimental preparation of the carrier and catalyst, as well as the use of the catalyst in the hydrotreating of hydrocarbon feedstocks, to illustrate the activity of the thus obtained catalysts. This information is for illustrative purposes only and is not intended to limit the invention in any way.

Examples

Activity test

[0042] Activity tests were conducted in flow microreactors. Light gas oil (LGO) enriched in dimethyl disulphide (DMDS) (total S content 2.5% wt.) was used for pre-sulfiding. Straight-run gas oil (SRGO), having a sulfur content of 1.4-1.1% of the mass. and an N content of 215-200 ppm was used for testing in Examples AE. VGO having an S content of 2.1 wt. and an N content of 1760 ppm was used in example F. The tests were carried out with the same volumetric flow of catalyst. The relative volumetric activities for various catalysts were determined as follows. For each catalyst, the volumetric reaction constant k _vol was calculated using nth order kinetics and reaction order 1.0 for HDN and 1.2 for HDS. The relative volumetric activities (RVA) of the various catalysts of the invention were then calculated, compared to the reference catalyst, based on the ratio of the reaction constants.

[0043] In the tables, SA is the surface area, PV is the pore volume, DMPD is the average pore diameter along the desorption branch of the physical adsorption isotherm N ₂ , S is sulfur, N is nitrogen, P is pressure, g _cat is the amount of catalyst in reactor, LHSV is the liquid hourly space velocity, and ro is the reaction order.

Getting Media

[0044] The following media were obtained in accordance with the procedures described below. One carrier was obtained as a reference (S1, Al ₂ O ₃ ). A summary of the properties of each media is shown in Table 1.

[0045] Example S1: Comparative S1. Comparative Example S1 was 100% standard Al ₂ O ₃ produced by a co-precipitation process. Aluminum sulfate (Alum) and sodium aluminate (Natal) were dosed simultaneously into a volume of water at 60° C. and pH 8.5. The Natal and Alum flows were fixed and the pH was constantly controlled with NaOH or H ₂ SO ₄ . The total dosing time was approximately 1 hour, and the final concentration of Al ₂ O ₃ in the reactor was approximately 4% by weight. The pH was then raised with NaOH or Natal to about 10 and the suspension was kept for 10 minutes with stirring. The suspension was filtered through a filter cloth and washed with water or a solution of ammonium bicarbonate in water until sufficient sodium and sulfate were removed. The cake was dried, extruded and calcined.

[0046] Example S2: carrier S2. Support S2 was obtained by co-extrusion of filter cakes of aluminum oxide and titanium dioxide. An alumina filter cake was prepared by the method described in Example S1 (prior to extrusion). A titanium dioxide filter cake was obtained by hydrolysis of an aqueous solution of TiOSO ₄ at 99°C for 5 h, followed by neutralization with NaOH to pH 7. The precipitate was filtered and washed from salts with water or ammonium bicarbonate solution. Two filter cakes were mixed in a kneader and extruded. The extrudates were calcined at 650°C for 1 hour in an air stream of approx. 10 n.l./min. It was found that in the final composition of the media (dry matter) was 49.7% of the mass. TiO ₂ and 50.3% wt. Al ₂ O ₃ .

[0047] Example S3: carrier S3. Support S3 was obtained using a co-precipitation process. Aluminum sulfate (Alum) and titanyl sulfate (TiOSO ₄ ), mixed in one stream, and sodium aluminate (Natal) were dosed simultaneously into a volume of water at 60° C. and pH 8.5. The flows of Natal and Alum/TiOSO ₄ were fixed and the pH was constantly controlled with NaOH or H ₂ SO ₄ . The total dosing time was approximately 1 hour and the final solids concentration in the reactor was approximately 4% by weight. The pH was then raised with NaOH or Natal to about 10 and the suspension was kept for 20 minutes with stirring. The suspension was filtered through a filter cloth and washed with water or a solution of ammonium bicarbonate in water until sufficient sodium and sulfate were removed. The cake was dried, extruded and calcined at 650°C for 1 hour in an air stream of approx. 10 n.l./min. It was found that in the final composition of the media (dry matter) was 48.0% of the mass. TiO ₂ and 52.0 wt%. Al ₂ O ₃ .

[0048] Example S4: carrier S4. The S4 support was obtained by co-precipitation using the same method used to prepare the S3 support, but with different amounts of TiO ₂ and Al ₂ O ₃ precursors. It was found that in the final composition of the media (dry matter) was 20.9% of the mass. TiO ₂ and 79.1% of the mass. Al ₂ O ₃ .

[0049] Example S5: carrier S5. Support S5 was obtained by successive (stepwise) deposition of alumina and titanium dioxide. First, alumina (boehmite) was deposited according to the procedure described in S1. After filtration and proper washing, the precipitate was transferred back to the reactor. The boehmite filter cake was suspended in a stainless steel vessel with water and stirred while heating to 60°C. The TiOSO ₄ solution was dosed into the suspension at a fixed rate and the pH was controlled at 8.5 by adding the NaOH solution. The dosing time was 25 min at 60°C. The slurry was thoroughly washed with water or ammonium bicarbonate in water to remove salts, dried, extruded and calcined at 650°C for 1 hour in an air stream of approx. 10 n.l./min. It was found that in the final composition of the media (on dry matter) was 21.1% of the mass. TiO ₂ and 78.9% of the mass. Al ₂ O ₃ .

[0050] Example S6: carrier S6. Support S6 was prepared by coating an aqueous titanium dioxide precursor on alumina extrudates. The extrudates used consisted primarily of γ-alumina and had a surface area of 271 m ² /g, a pore volume of 0.75 ml/g and an average pore diameter of 8.7 nm, as determined by the desorption branch of the N ₂ physical adsorption isotherm. The pores of the alumina extrudates were filled with an aqueous solution of titanium (IV) bis(ammonium lactate) dihydroxide, kept for 2 h at 60°C, and pre-dried on a rotating tray until the appearance of the extrudates was no longer wet, and finally dried in overnight at 120°C. The sample was calcined at 450°C for 2 h in an air stream. This procedure was repeated a second time, achieving higher concentrations of titanium dioxide. It was found that in the final composition of the media (dry matter) was 27.8% of the mass. TiO ₂ and 72.2% of the mass. Al ₂ O ₃ .

[0051] Example S7: Carrier S7. Support S7 was prepared by coating the alkoxide titanium dioxide precursor on alumina extrudates. The extrudates used had the same characteristics as the extrudates in S6. The pores of aluminum oxide were filled with a solution of Ti isopropoxide in propanol. The incubation process was carried out inside an atmospheric bag filled with N ₂ atmosphere at room temperature for 2 hours, and then the sample was placed outside the atmospheric bag for overnight hydrolysis (at RT). Finally, the sample was dried at 120° C. overnight and calcined at 450° C. for 2 hours. TiO ₂ and 81.1% of the mass. Al ₂ O ₃ .

[0052] Example S8: carrier S8. Support S8 was prepared by applying a second coating of an alkoxide titanium dioxide precursor to the TiO ₂ -Al ₂ O ₃ extrudates obtained in S7. The procedure described in S7 was repeated a second time, achieving higher concentrations of titanium dioxide. It was found that in the final composition of the media (dry matter) was 43.7% of the mass. TiO ₂ and 56.3% of the mass. Al ₂ O ₃ .

[0053] Example S9: carrier S9. Support S9 was obtained by "shock" deposition of aluminum oxide and titanium dioxide. Natal was diluted in water and liquid glass was added with vigorous stirring while heating at 60°C. To this mixture was added aluminum sulfate and titanyl sulfate over 20 minutes with a final pH of 6.5. NaOH was used to adjust the pH to 7.2 and the mixture was kept for 1 hour at 60° C. with stirring. The cake was resuspended with water, adjusted to pH 10 with ammonia, and kept at 95°C for 1 h with stirring. The suspension was then filtered and washed with water to remove excess ammonia, dried, extruded and calcined at 650° C. for 1 hour in an air stream of approx. 10 NL/min with 25 vol% water vapor. It was found that in the final composition of the media (dry matter) was 23.1% of the mass. TiO ₂ , 3.2% wt. SiO ₂ and 73.7% of the mass. Al ₂ O ₃ .

[0054] Example S10: carrier S10. Support S10 was prepared in the same manner as S9, using similar concentrations of the TiO ₂ source and lower concentrations for the SiO 2 source. It was found that in the final composition of the media (dry matter) was 21.3% of the mass. TiO ₂ , 0.5% wt. SiO ₂ and 78.2% of the mass. Al ₂ O ₃ .

[0055] Example S11: carrier S11. Support S11 was prepared in the same manner as S9, using lower concentrations of TiO ₂ and SiO ₂ sources. It was found that in the final composition of the media (dry matter) was 10.8% of the mass. TiO ₂ , 0.5% wt. SiO ₂ and 88.7% of the mass. Al ₂ O ₃ .

[0056] Example S12: carrier S12. Support S12 was obtained by co-extruding/kneading the Al ₂ O ₃ cake and the titanium source. After 15 minutes of mixing, titanium(IV) isopropoxide (source of titanium dioxide) was added. The outlet was then opened to allow the alcohol to evaporate. The kneaded material was extruded, and then the plate with wet extrudates was placed in an oven and kept there overnight at 120°C. Finally, the sample was calcined at 650° C. with 25% steam. It was found that in the final composition of the media (dry matter) was 10.6% of the mass. TiO ₂ , 0.87% wt. SiO ₂ and the rest - Al ₂ O ₃ .

[0057] The sodium content of any of these carriers was very low (<0.5% by weight) as it is known to impair hydroprocessing activity. A summary of the compositions and characteristics of these various carriers can be found in Table 1.

Table 1. Brief description of the media obtained in examples S1-S12, and some of their physical properties.

Carrier Methodology % wt.
TiO ₂ (*) % wt.
SiO ₂ (*) SA
(m ² /g) PV
(ml/g) DMPD (nm) S1 reference 0 - 271 0.84 8.1 S2 co-extrusion 47.9 - 200 0.52 8.7 S3 co-precipitation 48.0 - 258 0.64 7.7 S4 co-precipitation 20.9 - 304 0.86 7.9 S5 stepwise deposition 21.1 - 239 0.78 9.4 S6 coating 27.8 - 275 0.48 7.8 S7 coating 18.9 - 271 0.60 8.1 S8 coating 43.7 - 229 0.38 5.5 S9 "impact" deposition 23.1 3.2 293 0.56 6.1 S10 "impact" deposition 21.3 0.5 236 0.56 8.0 S11 "impact" deposition 10.8 0.5 240 0.65 9.0 S12 co-extrusion 10.6 0.87 247 0.54 6.7

(*) based on the total dry weight of the carrier

Preparation and testing of the catalyst

Example A: Positive effect of the addition of TiO ₂ in various amounts and in various preparation methods on the activity of NiMo catalysts

[0058] The following examples illustrate the positive effect of adding TiO ₂ to the media on the activity of NiMo catalysts in combination with sulfur-containing organic compounds in the preparation of the catalyst. Catalysts were prepared as described in Examples A1-A12, using the same method of supporting metals and S-organic additives on the catalysts, and at a comparable volume concentration of metals in the reactor. The catalysts were tested in a multi-reactor plant under medium pressure conditions with ultra-low sulfur diesel fuel with an equal volume of catalyst. Table 2 shows the presulfiding conditions and test conditions, and Table 3 shows the activity results.

Table 2. Presulfiding Conditions and Tests (ULSD, Average P) Used to Test the Activity of the NiMo Catalysts of Examples A.

Conditions for pre-sulfiding Raw material LHSV (h ^-1 ) P (bar/MPa) H ₂ /oil (n.l/l) Temperature (°C) Time (h) Enriched LGO 3 45/4.5 300 320 24 Test conditions Raw material P (bar/MPa) H ₂ /oil (n.l/l) Temperature (°C) Time @ condition (days) SRGO 1.09% wt. S and 200 ppm N 45/4.5 300 350 4

[0059] Example A1: Comparative A1. Comparative Example A1 was prepared by sequentially impregnating the support of Comparative Example A1 with (i) an aqueous solution of NiMoP and, after drying, (ii) thioglycolic acid. Both impregnations were carried out on a rotating tray. The metal intermediate was prepared from support S1 using impregnation with an amount of aqueous NiMoP solution equivalent to filling 105% of the pore volume, as known to one skilled in the art. The carrier pore volume was determined using the so-called water PV measurement, in which the initial moisture content was determined by adding water to the carrier extrudates. The NiMoP solution was prepared by dispersing the required amount of NiCO ₃ in water. The solution was then heated to 60° C. with stirring. Half of the required amount of H ₃ PO ₄ was carefully added to the solution, and then MoO ₃ was added in small portions. The solution was heated to 92°C to obtain a clear solution. Finally, the remainder of H ₃ PO ₄ was added to the solution and water was added to achieve the concentration required for the desired metal saturation. After impregnation, the extrudates were kept for 1 hour in a closed vessel, after which drying was carried out at 120° C. for at least 1 hour. Then, the impregnation of the thus obtained metal-saturated intermediate was carried out with pure thioglycolic acid to achieve a concentration of this compound on the catalysts 3.5 mol/mol metals (Mo+Ni) in the catalyst. The composite thus obtained was additionally kept for 2 hours while rotating. The extrudates were then poured into a Petri dish and placed in a static oven at 80° C. for 16 hours. MoO ₃ , 4.5% wt. NiO, 4.0% wt. P ₂ O ₅ , the rest is Al ₂ O ₃ .

[0060] Example A2: according to the invention A2. Inventive Example A2 was prepared using carrier S2 and the same preparation process as in A1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 17.2% of the mass. MoO ₃ , 3.3% wt. NiO, 3.1% wt. P ₂ O ₅ , 38.6% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[0061] Example A3: according to the invention A3. Inventive Example A3 was prepared using carrier S3 and the same preparation process as in A1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 19.4% of the mass. MoO ₃ and 3.8% wt. NiO, 3.5% wt. P ₂ O ₅ , 37.4% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[0062] Example A4: according to the invention A4. Inventive Example A4 was prepared using carrier S4 and the same preparation process as in A1. The composition impregnated with metal dried catalyst (dry matter) was 23.7% of the mass. MoO ₃ and 4.5% wt. NiO, 4.1% wt. P ₂ O ₅ , 13.0% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[0063] Example A5: according to the invention A5. Inventive Example A5 was prepared using carrier S5 and the same preparation process as in A1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 24.4% of the mass. MoO ₃ and 4.7% wt. NiO, 4.3% wt. P ₂ O ₅ , 13.5% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[0064] Example A6: according to the invention A6. Inventive Example A5 was prepared using carrier S5 and the same preparation process as in A1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 18.0% of the mass. MoO ₃ and 3.4% wt. NiO, 3.1% wt. P ₂ O ₅ , 21.2% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[0065] Example A7: according to the invention A7. Inventive Example A7 was prepared using S7 support and the same preparation process as in A1. The composition impregnated with metal dried catalyst (dry matter) was 20.1% of the mass. MoO₃ and 4.0 wt%. NiO, 3.5% wt. P₂O₅, 12.6% wt. TiO₂, and the rest - Al₂O₃.

[0066] Example A8: according to the invention A8. Inventive Example A8 was prepared using S8 support and the same preparation process as in A1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 18.7% of the mass. MoO ₃ and 3.7% wt. NiO, 3.4% wt. P ₂ O ₅ , 25.9% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[0067] Example A9: according to the invention A9. Inventive Example A9 was prepared using carrier S9 and the same preparation process as in A1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 18.0% of the mass. MoO ₃ and 3.5% wt. NiO, 3.3% wt. P ₂ O ₅ , 15.7% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[0068] Example A10: Comparative A10. Comparative Example A10 was prepared using S1 carrier and the same preparation process as in A1. The composition impregnated with metal dried catalyst (dry matter) was 24.8% of the mass. MoO ₃ and 4.4% wt. NiO, 4.3% wt. P ₂ O ₅ and the rest - Al ₂ O ₃ .

[0069] Example A11: according to the invention A11. Inventive Example A11 was prepared using carrier S10 and the same preparation process as in A1. The composition impregnated with metal dried catalyst (dry matter) was 22.0% of the mass. MoO₃ and 3.7% of the mass. NiO, 3.8% wt. P₂O₅, 0.37% wt. SiO₂, 15.0% wt. TiO₂, and the rest - Al₂O₃.

[0070] Example A12: according to invention A12. Inventive Example A12 was prepared using S11 support and the same preparation process as in A1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 23.6% of the mass. MoO₃ and 4.1% of the mass. NiO, 4.0% wt. P₂O₅, 0.36% wt. SiO₂, 7.4% wt. TiO₂, and the rest - Al₂O₃.

Table 3. Effect of adding TiO ₂ in combination with a sulfur-containing organic compound on the activity of supported NiMo catalysts in the activity test for ULSD, average P.

Example Carrier g _CAT dry
reactor mg MoO ₃
reactor LHSV
HDN N
(ppm) RVA
HDN
ro 1.0 LHSV
HDS S
(ppm) RVA
HDS
ro 1,2 comparative A1 S1 0.720 184 4.0 49 100% 2.5 151 100% according to invention A2 S2 0.881 168 40 108% 99 113% according to invention A3 S3 0.794 171 22 152% 42 151% according to the invention A4 S4 0.647 170 44 105% 119 107% according to invention A5 S5 0.640 173 35 123% 65 130% according to invention A6 S6 0.990 189 nine 211% 24 170% according to the invention A7 S7 0.844 184 nineteen 165% 33 169% according to the invention A8 S8 0.936 195 eleven 197% 28 171% according to the invention A9 S9 0.856 171 17 175% 38 155% comparative A10 S1 0.719 198 58 100% 2.7 144 100% according to invention A11 S10 0.855 209 nine 246% 24 177% according to invention A12 S11 0.820 215 nineteen 190% 29 169%

[0071] As can be seen from Table 3, the catalysts that were prepared using the Ti-containing support are significantly more active in HDN and HDS than the comparative catalyst without Ti (A1, A10), when using the same S-containing organic additive, the method impregnation and amount of metals in the reactor. Since different LHSVs were used, the RVAs of Inventive Examples A2-A9 are given relative to the activity of Comparative Example A1, and the RVAs of Inventive Examples A11-A12 are given relative to Comparative Example A10.

Examples B: Positive effect of the addition of TiO ₂ in different amounts and in different production methods on the activity of CoMo catalysts

[0072] These examples illustrate the positive effect of adding TiO ₂ to the media on the activity of CoMo catalysts in combination with sulfur-containing organic compounds at a wide range of TiO ₂ contents. All catalysts B1 - B10 were prepared using the same method of supporting metals and thioglycolic acid on the catalysts and at a comparable volumetric concentration of metals in the reactor. The catalysts were tested in a multi-reactor plant under medium pressure conditions with ultra-low sulfur diesel fuel. Table 4 shows pre-sulfiding conditions and Table 5 shows activity results.

Table 4. Presulfiding Conditions and Tests (ULSD, Average P) Used to Test the CoMo Activity of Example B Catalysts.

Conditions for pre-sulfiding Raw material LHSV
(h ^-1 ) P (bar/MPa) H ₂ /oil (n.l/l) Temperature (°C) Time (h) Enriched LGO 3 45/4.5 300 320 24 Test conditions Raw material P (bar/MPa) H ₂ /oil (n.l/l) Temperature (°C) Time @ condition (days) SRGO 1.09% wt. S and 200 ppm N 45/4.5 300 350 4

[0073] Example B1: Comparative B1. Comparative Example B1 was prepared by sequentially impregnating the support of Comparative Example A1 with (i) an aqueous solution of CoMoP and, after drying, (ii) thioglycolic acid. Both impregnations were carried out on a rotating tray. The metal intermediate was prepared from the S1 support using impregnation with an amount of an aqueous solution of CoMoP equivalent to filling 105% of the pore volume, as known to one skilled in the art. The carrier pore volume was determined using the so-called water PV measurement, in which the initial moisture content was determined by adding water to the carrier extrudates. The CoMoP solution was prepared by dispersing the required amount of CoCO ₃ in water. The solution was then heated to 60° C. with stirring. Half of the required amount of H ₃ PO ₄ was carefully added to the solution, and then MoO ₃ was added in small portions. The solution was heated to 92°C to obtain a clear solution. Finally, the remainder of H ₃ PO ₄ was added to the solution and water was added to achieve the concentration required for the desired metal saturation. After impregnation, the extrudates were kept for 1 hour in a closed vessel, after which drying was carried out at 120° C. for at least 1 hour. Then, the impregnation of the thus obtained metal-saturated intermediate was carried out with pure thioglycolic acid to achieve a concentration of this compound on the catalysts 3.5 mol/mol metals (Mo+Co) in the catalyst. The composite thus obtained was additionally kept for 2 hours while rotating. The extrudates were then poured into a Petri dish and placed in a static oven at 80° C. for 16 hours. MoO ₃ and 4.6% wt. CoO, 4.2% wt. P ₂ O ₅ and the rest is Al ₂ O ₃ .

[0074] Example B2: according to the invention B2. Inventive Example B2 was prepared using carrier S3 and the same preparation process as in B1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 19.1% of the mass. MoO ₃ and 3.6% wt. CoO, 3.3% wt. P ₂ O ₅ , 37.2% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[0075] Example B3: according to the invention B3. Inventive Example B3 was prepared using carrier S5 and the same preparation process as in B1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 19.8% of the mass. MoO ₃ and 3.8% wt. CoO, 3.3% wt. P ₂ O ₅ , 12.4% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[0076] Example B4: according to the invention B4. Inventive Example B4 was prepared using carrier S6 and the same preparation process as in B1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 19.1% of the mass. MoO ₃ and 3.6% wt. CoO, 3.3% wt. P ₂ O ₅ , 20.7% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[0077] Example B5: according to the invention B5. Inventive Example B5 was prepared using S7 support and the same preparation process as in B1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 19.8% of the mass. MoO ₃ and 3.8% wt. CoO, 3.5% wt. P ₂ O ₅ , 20.1% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[0078] Example B6: Comparative B6. Comparative example B6 was obtained using the carrier S1 and the same production process as in B1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 26.5% of the mass. MoO ₃ and 4.8% wt. CoO, 4.4% wt. P ₂ O ₅ and the rest is Al ₂ O ₃ .

[0079] Example B7: according to the invention B7. Inventive Example B7 was prepared using carrier S9 and the same preparation process as in B1. The composition impregnated with metal dried catalyst (dry matter) was 24.2% of the mass. MoO ₃ and 4.5% wt. CoO, 4.1% wt. P ₂ O ₅ , 1.8% wt. SiO ₂ , 13.9% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[0080] Example B8: Comparative B8. Comparative example B8 was obtained using the carrier S1 and the same production process as in B1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 26.1% of the mass. MoO ₃ and 4.8% wt. CoO, 4.4% wt. P ₂ O ₅ and the rest is Al ₂ O ₃ .

[0081] Example B9: according to the invention B9. Inventive Example B9 was prepared using S10 carrier and the same preparation process as in B1. The composition impregnated with metal dried catalyst (dry matter) was 23.4% of the mass. MoO₃ and 3.9% of the mass. CoO, 4.0% wt. P₂O₅, 0.36% wt. SiO₂, 14.7% wt. TiO₂, and the rest - Al₂O₃.

[0082] Example B10: according to the invention B10. Inventive Example B10 was prepared using the S11 carrier and the same preparation process as in B1. The composition impregnated with metal dried catalyst (dry matter) was 20.5% of the mass. MoO ₃ and 4.3% wt. CoO, 4.3% wt. P ₂ O ₅ , 0.36% wt. SiO ₂ , 7.2% wt. TiO ₂ and the rest is Al ₂ O ₃ .

Table 5. Effect of the addition of a sulfur-containing organic compound in combination with a TiO ₂ -containing support on the activity of CoMo catalysts in the activity test for ULSD, average P.

Example Carrier g _CAT dry
reactor mg MoO ₃
reactor LHSV
HDN N
(ppm) RVA HDN
ro 1 comparative B1 S1 0.730 194 3.5 fifty 100% according to invention B2 S3 0.837 180 26 158% according to invention B3 S5 0.829 182 34 131% according to invention B4 S6 0.919 187 21 160% according to invention B5 S7 0.891 196 20 174% comparative B6 S1 0.731 215 3.2 34 100% according to invention B7 S9 0.789 212 4 224% comparative B8 S1 0.701 203 4.0 88 100% according to invention B9 S10 0.893 232 nineteen 259% according to invention B10 S11 0.812 226 40 186%

[0083] As can be seen from Table 5, the catalysts that were prepared using Ti-containing supports (B2-B5, B7 and B9-B10) are significantly more active in HDN than the comparative catalysts without Ti (BB1, B6 and B8) , using the same S-organic additive and impregnation method. Because different LHSVs were used, the RVAs of Inventive Examples B2-B5 are shown relative to the activity of Comparative B1, the RVAs of Inventive Example B7 are shown relative to Comparative B6, and the RVAs of Inventive Examples B9-B10 are shown relative to Comparative B8.

Examples C: Positive effect of a wide range of S-organic additives on the activity of NiMo and CoMo catalysts

[0084] These examples illustrate the positive effect of S-organic additives on the activity of NiMo and CoMo catalysts in combination with a TiO ₂ -containing carrier. Examples of catalysts are 4 NiMo and 4 CoMo catalysts on the same Ti-Al support and with different organic sulfur additives. They were obtained using the same method of depositing metals and at a comparable volumetric concentration of metals in the reactor. The catalysts were tested in a multi-reactor plant under medium pressure conditions with ultra-low sulfur diesel fuel. Table 6 shows presulfiding conditions and test conditions for NiMo and CoMo catalysts, and Table 7 and Table 8 show activity results.

Table 6. Presulfiding Conditions and Tests (ULSD, Average P) Used to Test the Activity of the NiMo and CoMo Catalysts of Examples C.

Conditions for pre-sulfiding Raw material LHSV (h ^-1 ) P (bar/MPa) H ₂ /oil (n.l/l) Temperature (°C) Time (h) Enriched LGO 3 45/4.5 300 320 24 Test conditions Raw material P (bar/MPa) H ₂ /oil (n.l/l) Temperature (°C) Time @ condition (days) SRGO 1.09% wt. S and 200 ppm N 45/4.5 300 350 4

[0085] Example C1: Comparative C1. Comparative Example C1 was prepared by impregnating support S11 with an aqueous solution of NiMoP (without S-organic additive). The impregnation was carried out on a rotating pan with an amount of aqueous NiMoP solution equivalent to filling 105% of the pore volume, as known to the person skilled in the art. The carrier pore volume was determined using the so-called water PV measurement, in which the initial moisture content was determined by adding water to the carrier extrudates. The NiMoP solution was prepared by dispersing the required amount of NiCO ₃ in water. The solution was then heated to 60° C. with stirring. Half of the required amount of H ₃ PO ₄ was carefully added to the solution, and then MoO ₃ was added in small portions. The solution was heated to 92°C to obtain a clear solution. Finally, the remainder of H ₃ PO ₄ was added to the solution and water was added to achieve the concentration required for the desired metal saturation. After impregnation, the extrudates were kept for 1 hour in a closed vessel, after which they were dried at 120°C for at least 1 hour. The extrudates were then poured into a Petri dish and placed in a static oven at 80°C for 16 hours. the metal of the dried catalyst (dry matter) was 23.6% of the mass. MoO ₃ and 4.1% wt. NiO, 4.0% wt. P ₂ O ₅ , 0.36% wt. SiO ₂ , 7.4% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[0086] Example C2: according to the invention C2. Inventive Example C2 was prepared using Comparative Example C1. The second impregnation with thiolactic acid at 95% PV saturation was carried out without the use of H ₂ O and kept for 2 h at 80°C. The extrudates were then poured into a Petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal impregnated dried catalyst (on a dry matter basis) was the same as in Comparative Example C1.

[0087] Example C3: according to the invention C3. Inventive Example C3 was prepared using Comparative Example C1. The second impregnation with 3-mercaptopropionic acid was carried out with a fixed amount, reaching 15% of the mass. carbon from the total mass of the catalyst, and kept for 2 h at 80°C. The extrudates were then poured into a Petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal-impregnated dried catalyst (on a dry matter basis) was the same as in Comparative Example C1.

[0088] Example C4: according to the invention C4. Inventive Example C4 was prepared using Comparative Example C1. The second impregnation with mercaptosuccinic acid was carried out with a fixed amount, reaching 15% of the mass. carbon from the total mass of the catalyst, and kept for 2 h at 80°C. The extrudates were then poured into a Petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal-impregnated dried catalyst (on a dry matter basis) was the same as in Comparative Example C1.

Table 7. Effect of the addition of a sulfur-containing organic compound in combination with a TiO ₂ -containing support on the activity of NiMo catalysts in the activity test for ULSD, average P.

Example Carrier g _CAT dry
reactor mg MoO ₃
reactor LHSV
HDN N
(ppm) RVA HDN
ro 1 LHSV
HDS S
(ppm) RVA HDS
ro 1,2 comparative C1 S11 0.787 206 4.0 66 100% 2.7 175 100% according to the invention C2 S11 0.770 202 40 153% 65 147% according to invention C3 S11 0.768 201 56 116% 104 120% according to the invention C4 S11 0.780 205 46 124% 74 128%

[0089] As can be seen from Table 7, NiMo catalysts with various types of S-containing organic additives (C2-C4) show higher activity in HDN and HDS than Comparative Example (C1) without organic additives using the same support ( S11) and similar concentrations of metal (about 200 g MoO ₃ /reactor).

[0090] Example C5: Comparative C5. Comparative Example C5 was prepared from carrier S11 using impregnation with an amount of an aqueous solution of CoMoP equivalent to filling 105% of the pore volume, as known to one skilled in the art. The CoMoP solution was prepared by dispersing the required amount of CoCO₃ in water. The solution was then heated to 60° C. with stirring. Half the required amount of H₃PO₄ was carefully added to the solution, and then MoO was added in small portions₃. The solution was heated to 92°C to obtain a clear solution. Finally, the remainder of H was added to the solution.₃PO₄ and water was added to achieve the concentration necessary for the desired metal saturation. After impregnation, the extrudates were kept for 1 hour in a closed vessel, after which they were dried at 120°C for at least 1 hour. The extrudates were then poured into a Petri dish and placed in a static oven at 80°C for 16 hours. the metal of the dried catalyst (on dry basis) was 23.2% of the mass. MoO₃, 3.9 wt%. CoO, 2.4% wt. P₂O₅, 0.37% wt. SiO₂, 7.5 wt%. TiO₂, and the rest - Al₂O₃.

[0091] Example C6: according to the invention C6. Inventive Example C6 was prepared using Comparative Example C5. The second impregnation with thiolactic acid at 95% PV saturation was carried out without the use of H ₂ O and kept for 2 h at 80°C. The extrudates were then poured into a Petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal-impregnated dried catalyst (on a dry matter basis) was the same as in Comparative Example C5.

[0092] Example C7: according to the invention C7. Inventive Example C7 was prepared using Comparative Example C5. The second impregnation with 3-mercaptopropionic acid was carried out with a fixed amount, reaching 15% of the mass. carbon from the total weight of the dried catalyst, and kept for 2 h at 80°C. The extrudates were then poured into a Petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal-impregnated dried catalyst (on a dry matter basis) was the same as in Comparative Example C5.

[0093] Example C8: according to the invention C8. Inventive Example C8 was prepared using Comparative Example C5. The second impregnation with mercaptosuccinic acid was carried out with a fixed amount, reaching 15% of the mass. carbon from the total weight of the dried catalyst, and kept for 2 h at 80°C. The extrudates were then poured into a Petri dish and placed in a static oven at 80° C. for 16 hours. The composition of the metal-impregnated dried catalyst (on a dry matter basis) was the same as in Comparative Example C5.

Table 8. Effect of the addition of a sulfur-containing organic compound in combination with a TiO ₂ -containing support on the activity of CoMo catalysts in the activity test for ULSD, average P.

Example Carrier g _CAT dry
reactor mg MoO ₃ reactor LHSV
HDN N
(ppm) RVA HDN
ro 1 comparative C5 S11 0.77 197 4.0 89 100% according to the invention C6 S11 0.79 203 52 158% according to the invention C7 S11 0.8 223 63 137% according to the invention C8 S11 0.77 197 74 116%

[0094] As can be seen from Table 8, CoMo catalysts with various types of S-containing organic additives (C6-C8) show higher HDN activity than Comparative Example (C5) without organic additives using the same carrier (S11) and similar concentrations of metal (about 200 g MoO ₃ /reactor).

Examples D: Synergistic effect of sulfur-containing organic compounds and Ti-Al ₂ O ₃ support for NiMo catalysts

[0095] The following examples show that the use of TiO ₂ /Al ₂ O ₃ support in combination with S-organic compounds leads to a synergistic effect for NiMo catalysts. The increase in activity due to the use of TiO ₂ /Al ₂ O ₃ carrier in combination with S-organic compounds is higher than would be expected from the individual contributions of (i) TiO ₂ /Al ₂ O ₃ carrier and (ii) S- organic compounds, as determined in separate experiments, and therefore may be considered unexpected. The examples of NiMo catalyst shown have comparable metal concentrations and were tested in a multi-reactor plant with ultra-low sulfur diesel fuel under medium pressure conditions. Table 9 lists the experimental parameters for the presulfiding conditions and test conditions, and Table 10 shows the amount of catalyst that was loaded into the different reactors and the activity results.

Table 9. Presulfiding Conditions and Tests (ULSD, Average P) Used to Test the Activity of the NiMo Catalysts of Examples D.

Conditions for pre-sulfiding Raw material LHSV (h ^-1 ) P (bar/MPa) H ₂ /oil (n.l/l) Temperature (°C) Time (h) Enriched LGO 3 45/4.5 300 320 24 Test conditions Raw material P (bar/MPa) H ₂ /oil (n.l/l) Temperature (°C) Time @ condition (days) SRGO 1.09% wt. S and 200 ppm N 45/4.5 300 350 4

[0096] Example D1: Comparative D1. Comparative example D1 was prepared using support S1 and impregnated with an aqueous solution of NiMoP, without organic additive. The method used to prepare the impregnating solution is the same as that described in Example C1. The composition impregnated with metal dried catalyst (dry matter) was 24.8% of the mass. MoO ₃ , 4.2% wt. NiO, 2.7% wt. P ₂ O ₅ and the rest is Al ₂ O ₃ .

[0097] Example D2: Comparative D2. Comparative example D2 was prepared using carrier S1 and impregnated with an aqueous solution of NiMoP and the addition of thioglycolic acid. The method used to prepare the impregnating solution and the amount of S-organic compounds used (relative to metals) is the same as the method described in example A1. The composition of the dried metal-impregnated catalyst (on a dry matter basis) was the same as in D1.

[0098] Example D3: Comparative D3. Comparative example D3 was prepared using support S10 and impregnated with an aqueous solution of NiMoP, without organic additive. The method used to prepare the impregnating solution is the same as that described in Example C1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 21.8% of the mass. MoO ₃ , 3.6% wt. NiO, 2.4% wt. P ₂ O ₅ , 0.38% wt. SiO ₂ , 15.4% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[0099] Example D4: according to the invention D4. Inventive Example D4 was prepared using S10 support and impregnated with an aqueous solution of NiMoP and an addition of thioglycolic acid. The method used to prepare the impregnating solution and the amount of S-organic compounds used (relative to metals) is the same as the method described in example A1. The composition of the dried metal-impregnated catalyst (on a dry matter basis) was the same as in Example D3.

[00100] Example D5: Comparative D5. Comparative example D5 was prepared using support S11 and impregnated with an aqueous solution of NiMoP, without organic additive. The method used to prepare the impregnating solution is the same as that described in Example C1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 23.3% of the mass. MoO ₃ , 3.7% wt. NiO, 2.5% wt. P ₂ O ₅ , 0.38% wt. SiO ₂ , 7.6% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[00101] Example D6: according to the invention D6. Inventive Example D6 was prepared using support S11 and impregnated with an aqueous solution of NiMoP and an addition of thioglycolic acid. The method used to prepare the impregnating solution and the amount of S-organic compounds used (relative to metals) is the same as the method described in example A1. The composition of the dried metal-impregnated catalyst (on a dry matter basis) was the same as in Example D5.

Table 10. Effect of the addition of a sulfur-containing organic compound in combination with a TiO ₂ -containing support on the activity of NiMo catalysts in the activity test for ULSD, average P.

Example Carrier g _CAT dry
reactor mg MoO ₃
reactor LHSV
HDN N
(ppm) RVA
HDN
ro 1 Sxy
HDN LHSV HDS S
(ppm) RVA
HDS
ro 1,2 Sxy
HDS comparative D1 S1 0.710 196 4.0 87 100% 2.7 261 100% comparative D2 S1 0.713 197 67 121% 183 110% comparative D3 S10 0.829 201 53 141% 94 135% according to invention D4 S10 0.847 205 6 370% 208 20 221% 76 comparative D5 S11 0.762 197 73 114% 211 106% according to invention D6 S11 0.793 205 23 218% 83 29 192% 76

[00102] As can be seen from Table 10, the activity gain of the catalysts of the invention (D4 and D6) containing TiO ₂ in the media and S-containing organic compounds is greater than expected based on the individual benefits of adding titanium dioxide (D3 and D5 , without S-organic additive) or using S-organic additive (D2, without titanium dioxide). Both examples according to the invention are ultimately compared with comparative example D1 (without organic compounds and without titanium dioxide) at the same metal concentrations.

[00103] To determine the degree of synergy between the effect of (i) adding TiO ₂ to the support and (ii) adding S-containing organic compounds on catalyst activity, the inventors determined the synergy coefficient Sxy as defined in equation 1. RVA _0.0 is relative activity of the reference catalyst (without Ti (x) or organic compounds (y)). The values for ax and by were determined from the RVA of a comparative catalyst based on Al ₂ O ₃ -support with the same organic compounds (RVA _x.0 =RVA _0.0 +ax) and the RVA of a comparative catalyst based on TiO ₂ -Al ₂ O ₃ -carrier without organic compounds (RVA _0,y =RVA _0.0 +by). A positive Sxy value means that the activity of the catalysts of the invention is higher than would be expected based on the individual contributions of the support and organic compounds to the activity of the catalyst.

RVAx, y=RVA _0.0 +ax+by+Sxy (Lv.1)

Examples E: Synergistic Effect of Organosulfur Compounds and Ti-Al ₂ O ₃ Support for CoMo Catalysts

[00104] The following examples show that the use of TiO ₂ /Al ₂ O ₃ support in combination with S-organic compounds results in a synergistic effect for CoMo catalysts over a wide range of metal concentrations. The increase in activity due to the use of TiO ₂ /Al ₂ O ₃ carrier in combination with S-organic compounds is higher than would be expected from the individual contributions of (i) TiO ₂ /Al ₂ O ₃ carrier and (ii) S- organic compounds, as determined in separate experiments, and therefore may be considered unexpected. The examples of CoMo catalyst shown were tested in a multi-reactor plant with ultra-low sulfur diesel fuel under medium pressure conditions. A group of examples was tested at a comparable metal volume concentration. The first group - with a high metal concentration (examples E1-E4) and the second group - with a low metal concentration (examples E5-E8). Table 11 and Table 13 show the experimental parameters of the presulfiding conditions and test conditions, and Table 12 and Table 14 show the amount of catalyst that was loaded into the different reactors and the activity results.

[00105] Example E1: Comparative E1. Comparative example E1 was prepared using support S1 and impregnated with an aqueous solution of CoMoP, without organic additive. The method used to prepare the impregnation solution was the same as that described in Example C5. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 24.6% of the mass. MoO ₃ , 4.3% wt. CoO, 2.6% wt. P ₂ O ₅ and the rest is Al ₂ O ₃ .

[00106] Example E2: Comparative E2. Comparative example E2 was prepared using carrier S1 and impregnated with an aqueous solution of CoMoP and the addition of thioglycolic acid. The method used to prepare the impregnating solution is the same as the method described in Example B1. The composition of the dried metal-impregnated catalyst (on a dry matter basis) was the same as in E1.

[00107] Example E3: Comparative E3. Comparative Example E3 was prepared using S11 carrier and impregnated as in the method described in Example E1. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 21.8% of the mass. MoO ₃ , 3.7% wt. CoO, 2.3% wt. P ₂ O ₅ , 0.38% wt. SiO ₂ , 15.2% wt. TiO ₂ and the rest is Al ₂ O ₃ .

[00108] Example E4: according to the invention E4. Example according to the invention E4 was obtained using support S11 and impregnated as in the method described in example E1. The composition of the dried metal-impregnated catalyst (on a dry matter basis) was the same as in Example E3.

Table 11. Presulfiding Conditions and Tests (ULSD, Average P) Used to Test the Activity of the High Metal CoMo Catalysts of Examples E.

Conditions for pre-sulfiding Raw material LHSV (h ^-1 ) P (bar/MPa) H ₂ /oil (n.l/l) Temperature (°C) Time (h) Enriched LGO 3 45/4.5 300 320 24 Test conditions Raw material P (bar/MPa) H ₂ /oil (n.l/l) Temperature (°C) Time @ condition (days) SRGO 1.09% wt. S and 200 ppm N 45/4.5 300 350 4

Table 12. Effect of the addition of a sulfur-containing organic compound in combination with a TiO ₂ -containing support on the activity of CoMo catalysts with a high metal concentration in the activity test for ULSD, average P.

Example Carrier g _CAT dry
reactor mg MoO ₃
reactor LHSV
HDN N
(ppm) RVA HDN
ro 1 Sxy
HDN comparative E1 S1 0.682 186 4.0 100 100% comparative E2 S1 0.701 192 81 132% comparative E3 S10 0.829 201 67 145% by invention E4 S10 0.83 201 37 226% 49

[00109] As can be seen from Table 12, the benefit in activity of the catalysts of the invention (E4) is greater than expected based on the individual benefits of adding titanium dioxide (E3, without S-organic additive) or using S-organic additive (E2, without titanium dioxide). The activities of all catalysts were ultimately compared to Comparative Example E1 (no organics and no titanium dioxide) at the same metal concentrations.

[00110] Example E5: Comparative E5. Comparative example E5 was prepared using support S1 and impregnated as E1 with an organic-free aqueous solution of CoMoP. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 19.3% of the mass. MoO ₃ and 3.6% wt. CoO, 3.2% wt. P ₂ O ₅ and the rest is Al ₂ O ₃ .

[00111] Example E6: Comparative E6. Comparative Example E6 was prepared using S9 carrier and impregnated as for E5. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 17.5% of the mass. MoO₃ and 3.2% of the mass. CoO, 2.9% wt. P₂O₅, 15.8% wt. TiO₂, 2.0% wt. SiO₂, and the rest - Al₂O₃.

[00112] Example E7: Comparative E7. Comparative example E7 was prepared using carrier S1. It was first impregnated with an aqueous solution of CoMoP as E1 and after drying, a second impregnation with thioglycolic acid (3.5 mol/mol metals in the catalyst) was carried out in a rotating pan. The intermediate product was further kept for 2 hours with rotation and then poured into a Petri dish and placed in a static oven at 80° C. for 16 hours. MoO ₃ and 3.6% wt. CoO, 3.2% wt. P ₂ O ₅ and the rest is Al ₂ O ₃ .

[00113] Example E8: according to the invention E8. Inventive example E8 was prepared using carrier S9 and impregnated as for E7. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 17.5% of the mass. MoO ₃ and 3.2% wt. CoO, 2.9% wt. P ₂ O ₅ , 15.7% wt. TiO ₂ and 2.1% wt. SiO2 _.

Table 13. Presulfiding Conditions and Tests (ULSD, Average P) Used to Test the Activity of CoMo Catalysts with Low Metal Concentration of Examples E.

Conditions for pre-sulfiding Raw material LHSV (h ^-1 ) P (bar/MPa) H ₂ /oil (n.l/l) Temperature (°C) Time (h) Enriched LGO 3 45/4.5 300 320 24 Test conditions Raw material P (bar/MPa) H ₂ /oil (n.l/l) Temperature (°C) Time @ condition (days) SRGO 1.4% wt. S and 200 ppm N 45/4.5 300 350 3

Table 14. Effect of the addition of a sulfur-containing organic compound in combination with a TiO2-containing support on the activity of CoMo catalysts with low metal concentration in the activity test for ULSD, average P.

Example Carrier g _CAT dry
reactor mg MoO ₃
reactor LHSV
HDN N
(ppm) RVA
HDN
ro 1 Sxy
HDN LHSV
HDS S
(ppm) RVA
HDS
ro 1,2 Sxy
HDS comparative E5 S1 0.634 136 2.6 86 100% 2.0 244 100% comparative E6 S9 0.736 143 2.6 38 192% 119 126% comparative E7 S1 0.611 131 2.8 68 129% 143 108% by invention E8 S9 0.714 139 2.8 7 362% 141 24 172% 38 commercial CoMo catalyst 0.731 196 2.6 27 235% fifty 161% commercial CoMo catalyst 0.742 196 2.8 28 235% 41 161%

[00114] In the case of catalysts with a low concentration of metals, a synergistic effect is also observed between the carrier and organic compounds. This is unexpected since neither TiO ₂ nor the organic materials used in the preparation will directly contribute to the activity of the catalysts. This effect is clearly seen over a wide range of metal concentrations (high about 220 g MoO ₃ /l and low about 140 g MoO ₃ /l) and is most easily seen for HDN activity. Finally, the activity of the low metal catalyst of the invention (E8) can be compared with that of a commercial CoMo catalyst which was included in the same test.

Examples F: Benefit of TiO ₂ -Al ₂ O ₃ Co-Extruded Support in Combination with S-Organic Additives for NiMo Catalysts under HC-RT Conditions

[00115] The following examples illustrate the positive effect of adding TiO ₂ to the media on the activity of NiMo catalysts in combination with S-containing organic compounds in the preparation of the catalyst. Catalysts were prepared as described in Examples F1-F2 using the same method of supporting metals on the catalysts and at comparable volume concentrations of metals in the reactor. The catalysts were tested in a multi-reactor setup under HC-PT conditions. Table 15 shows the presulfiding conditions and test conditions, and Table 16 shows the activity results.

Table 15. Presulfiding Conditions and Tests (HC-PT) Used to Test the Activity of Low Metal NiMo Catalysts of Examples F.

Conditions for pre-sulfiding Raw material LHSV (h ^-1 ) P (bar/MPa) H ₂ /oil (n.l/l) Temperature (°C) Time (h) Enriched LGO 3 45/4.5 300 320 24 Test conditions Raw material P (bar/MPa) H ₂ /oil (n.l/l) Temperature (°C) Time @ condition (days) VGO 2.1% wt. S and 1760 ppm N 120/12.0 1000 380 3

[00116] Example F1: Comparative F1. Comparative example F1 was prepared using support S1 and an aqueous solution of NiMoP. The catalyst was prepared on the basis of support S1 impregnated with an amount of an aqueous solution of NiMoP equivalent to filling 105% of the pore volume, as known to a person skilled in the art. The carrier pore volume was determined using the so-called water PV measurement, in which the initial moisture content was determined by adding water to the carrier extrudates. The NiMoP solution was prepared by dispersing the required amount of NiCO ₃ in water. The solution was then heated to 60° C. with stirring. Half of the required amount of H ₃ PO ₄ was carefully added to the solution, and then MoO ₃ was added in small portions. The solution was heated to 92°C to obtain a clear solution. Finally, the remainder of H ₃ PO ₄ was added to the solution and water was added to achieve the concentration required for the desired metal saturation. After impregnation, the extrudates were kept for 1 hour in a closed vessel, after which they were dried at 120°C for at least 1 hour. The extrudates were then poured into a Petri dish and placed in a static oven at 80°C for 16 hours. the metal of the dried catalyst (on dry basis) was 25.9% of the mass. MoO ₃ , 4.1% wt. NiO, 4.4% wt. P ₂ O ₅ and the rest is Al ₂ O ₃ .

[00117] Example F2: according to the invention F2. Example of the Invention F2 was prepared from support S12 impregnated with an amount of aqueous NiMoP solution equivalent to filling 105% of the pore volume, as known to the person skilled in the art. The carrier pore volume was determined using the so-called water PV measurement, in which the initial moisture content was determined by adding water to the carrier extrudates. The NiMoP solution was prepared by dispersing the required amount of NiCO ₃ in water. The solution was then heated to 60° C. with stirring. Half of the required amount of H ₃ PO ₄ was carefully added to the solution, and then MoO ₃ was added in small portions. The solution was heated to 92°C to obtain a clear solution. Finally, the remainder of H ₃ PO ₄ was added to the solution and water was added to achieve the concentration required for the desired metal saturation. After impregnation, the extrudates were kept for 1 hour in a closed vessel, after which drying was carried out at 120°C for at least 1 hour. The extrudates were then poured into a Petri dish and placed in a static oven at 80°C for 16 hours. the thus metal-saturated intermediate was run with pure thioglycolic acid to achieve a concentration of this compound on the catalysts of 3.5 mol/mol metals (Mo+Ni) in the catalyst. The composite thus obtained was additionally kept for 2 hours while rotating. In the composition of the dried catalyst impregnated with metal (on a dry matter basis) was 24.1% of the mass. MoO ₃ , 4.0% wt. NiO, 4.1% wt. P ₂ O ₅ , 7.2% wt. TiO ₂ , 0.59% wt. SiO ₂ and the rest is Al ₂ O ₃ .

Table 16. Effect of addition of an organic compound in combination with a TiO ₂ -containing support on the activity of NiMo catalysts when testing activity under HC-PT conditions.

Example Carrier g _CAT dry
reactor mg MoO ₃
reactor LHSV
HDN N
(ppm) RVA
HDN
ro 1 comparative F1 S1 0.719 186 1.70 182 100 according to the invention F2 S12 0.940 226 57 156

[00118] As can be seen from Table 16, Inventive Example F2, containing S-organic additives and supported titanium, exhibits superior benefits in both HDN and HDS than Comparative Example F1. The advantage of the combination of S-organic additive and Ti-containing carrier is also seen for HC-PT applications.

[00119] Components named by their chemical names or formula, throughout the text of the description or formula of this application, specified in the plural or singular, are identified as they existed before being brought into contact with another substance given under its chemical name or chemical type (eg, other component, solvent, etc.). It does not matter what chemical changes, transformations and/or reactions took place (if any) in obtaining the resulting mixture or solution, if such changes, transformations and/or reactions are the natural result of contacting these components with each other under the conditions provided for in this description. Thus, the components are defined as ingredients for bringing into contact with each other in connection with the performance of the required operations or in the formation of the desired composition.

[00120] This invention may contain, consist of, or consist essentially of the materials and/or procedures described in this application.

[00121] As used herein, the term "about", modifying the amount of an ingredient in the compositions of the invention or involved in the methods of the invention, refers to variations in the numerical amount that can occur, for example, when using conventional methods of measuring and working with liquids used for preparation of concentrates or use of solutions in practice, as a result of inadvertent error in these methods, differences in the manufacturing process, the source or purity of the ingredients used in the preparation of the compositions or the implementation of the methods, and the like. The term "about" also means amounts that differ due to different balancing conditions of the composition due to the use of a certain initial mixture. Whether modified by the term "about" or not, the claims include the equivalents of these amounts.

[00122] Except where it may be expressly stated otherwise, the reference to the singular, if present and used in this application, is not intended to be limiting and should not be construed as limiting the description or claim to the single element to to which it applies. Rather, the reference to the singular, if present and used in this application, is intended to include one or more of these elements, unless the text clearly states otherwise.

[00123] Without exception, all patents or other publications or published documents that relate to any part of this application are incorporated into this application by reference in their entirety, as if they were fully set forth in this application.

[00124] This invention is subject to significant variations in its implementation in practice. Therefore, the above description is not intended to be limiting and should not be construed as limiting the invention to the specific illustrative examples presented herein above.

Claims (34)

1. A catalyst for the hydrotreatment of hydrocarbon feedstock after its conversion into a sulfided form, containing: at least one component containing a Group VIB metal selected from molybdenum and tungsten, at least one component containing a Group VIII metal selected from nickel and cobalt, at least one component in the form of a sulfur-containing organic additive selected from the group consisting of thiolactic acid, mercaptosuccinic acid and cysteine, and a component representing a titanium-containing carrier, additionally containing alumina, where the amount of the titanium component is in the range of 1-60% wt., expressed as oxide (TiO ₂ ), based on the total weight of the catalyst and where at least one component in the form of a sulfur-containing organic additive is present in an amount of 1-30% wt. WITH. 2. The catalyst of claim 1, wherein the amount of the Group VIB metal is in the range of 15-30 wt %, expressed as oxide, based on the total weight of the catalyst. 3. The catalyst of claim 1, wherein the amount of the Group VIII metal is in the range of 2-8 wt %, expressed as oxide, based on the total weight of the catalyst. 4. The catalyst of claim 1 wherein the Group VIB metal is molybdenum and the Group VIII metal is nickel and/or cobalt. 5. The catalyst according to claim 1, also containing a component in the form of phosphorus in the amount of 1-8 wt. -%, expressed as an oxide, based on the total weight of the catalyst. 6. The catalyst according to claim 1, in which at least one component in the form of a sulfur-containing organic additive is present in an amount of 1-20% of the mass. WITH. 7. The catalyst according to claim 6, in which at least one component in the form of a sulfur-containing organic additive is present in an amount of 5-15% of the mass. WITH. 8. A method for producing a catalyst according to claim 1, intended for subsequent conversion into a sulfided form for the hydrotreatment of hydrocarbon feedstock, including coextruding a titanium source with a porous material containing Al ₂ O ₃ to form an extrudate of a titanium-containing carrier, drying and calcining the extrudate and impregnating the calcined extrudate with a sulfur-containing organic additive selected from the group consisting of thiolactic acid, mercaptosuccinic acid and cysteine, with at least one source of a Group VIB metal selected from molybdenum and tungsten, and at least one source of a Group VIII metal selected from nickel and cobalt, moreover, the amount of titanium source is sufficient to form a catalyst composition having at least a titanium content in the range of 1-60 wt. -%, expressed as oxide (TiO ₂ ), based on the total weight of the catalyst. 9. A method for producing a catalyst according to claim 1, intended for subsequent conversion into a sulfided form for the hydrotreatment of hydrocarbon feedstock, including deposition of a source of titanium with a source of aluminum, extruding the precipitate to form an extrudate of a titanium-containing carrier, drying and calcining the extrudate, and impregnating the calcined extrudate with a sulfur-containing organic additive selected from the group consisting of thiolactic acid, mercaptosuccinic acid and cysteine, with at least one source of a Group VIB metal selected from molybdenum and tungsten, and at least one source of a Group VIII metal selected from nickel and cobalt, moreover, the amount of titanium source is sufficient to form a catalyst composition having at least a titanium content in the range of 1-60 wt. -%, expressed as oxide (TiO ₂ ), based on the total weight of the catalyst. 10. The method of claim 9 wherein the precipitation comprises the steps of (a) simultaneously dosing sodium aluminate and aluminum sulfate into water at a fixed pH, (b) resuspending the formed alumina filter cake in water, (c) adding TiOSO to this suspension ₄ or titanium sulfate at a fixed pH>7 controlled by an alkaline solution. 11. The method of claim 9, wherein the source of aluminum and the source of titanium are mixed in the same stream and sodium aluminate is dosed either simultaneously or sequentially into water at pH>7. 12. A method for producing a catalyst according to claim 1, intended for subsequent conversion into a sulfided form for the hydrotreatment of hydrocarbon feedstock, including impregnation of a porous material containing Al ₂ O ₃ with a source of titanium to form a titanium-containing carrier, drying and calcining the support and impregnation of the calcined support with a sulfur-containing organic additive selected from the group consisting of thiolactic acid, mercaptosuccinic acid and cysteine, at least one source of a Group VIB metal selected from molybdenum and tungsten, and at least one source of a Group VIII metal selected from nickel and cobalt, moreover, the amount of titanium source is sufficient to form a catalyst composition having at least a titanium content in the range of 1-60 wt. -%, expressed as oxide (TiO ₂ ), based on the total weight of the catalyst. 13. The method according to claim 8, 9 or 12, further comprising impregnation with a sulfur-containing organic additive, at least one source of a group VIB metal and / or at least one source of a group VIII metal, which is carried out in one stage using a solution containing sulfur-containing an organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source. 14. The method according to claim 8, 9 or 12, further comprising impregnation with a sulfur-containing organic additive, at least one source of a group VIB metal and/or at least one source of a group VIII metal, which is carried out in more than one stage, while the carrier is impregnated with a solution containing at least one Group VIB metal source and/or at least one Group VIII metal source, followed by the step of impregnating the carrier with a solution containing a sulfur-containing organic additive. 15. The method according to claim 8, 9 or 12, wherein the titanium source is selected from the group consisting of titanyl sulfate, titanium sulfate, titanium alkoxide, or titanium (IV) bis(ammonium lactate) dihydroxide. 16. A method for hydrotreating a hydrocarbon feed, which includes presulfiding the catalyst according to any one of claims 1 to 7 or obtained using the method according to any of claims 8 to 15 and contacting the hydrocarbon feed with the presulfided catalyst under hydrotreating conditions to hydrotreat the hydrocarbon feed.