Method for activating a catalytically active material
Patent Information
- Application Number
- BR112022011996
- Authority / Receiving Office
- BR · BR
- Patent Type
- Patents
- Current Assignee / Owner
- Publication Date
- 2026-08-25
Abstract
Description
METHOD FOR ACTIVATING A CATALYTICALLY ACTIVE MATERIAL
[001] The present invention relates to a method for activating a hydrotreating catalyst or a hydroprocessing catalyst. The hydrotreating catalyst to be activated may be a fresh hydrotreating catalyst or a hydrotreating catalyst that has been used and subsequently regenerated. The present invention also relates to the hydrotreating catalyst obtained by said process and its use in hydrotreating. Furthermore, the present invention relates to similar processes applied to other hydroprocessing catalysts, such as isomerization and hydrocracking catalysts, and such resulting catalysts.
[002] In general, the objective of catalytically hydrotreating foods containing hydrocarbons is the removal of impurities. Common impurities are sulfur compounds and nitrogen compounds. The removal, at least partial, of such impurities from a food will ensure that, once the final product is burned, fewer sulfur oxides and / or nitrogen oxides harmful to the environment will be released. Furthermore, sulfur compounds and nitrogen compounds are toxic to many of the catalysts employed in the refining industry to convert foods into ready-to-use products. Examples of such catalysts include cracking catalysts, hydrocracking catalysts, and reforming catalysts. It is therefore common for foods to undergo catalytic hydrotreatment before being processed in, for example, a cracking unit.Catalytic hydrotreating involves bringing a food into contact with hydrogen at high temperature and pressure in the presence of a hydrotreating catalyst. In this process, sulfur compounds and nitrogen compounds present in the food are converted into easily removable hydrogen sulfide and ammonia. Petition 870250015802, dated 26 / 02 / 2025, page 17 / 36 2 / 10
[003] In general, hydrotreating catalysts comprise a carrier with a Group VI metal component and a Group VIII metal component deposited on it. The most commonly used Group VI metals are molybdenum and tungsten, while cobalt and nickel are the conventional Group VIII metals. Phosphorus and other elements may also be present in the catalyst. State-of-the-art processes for the preparation of these catalysts are characterized by a carrier material being compounded with hydrogenated metal components, for example by impregnation, after which the composite is calcined to convert the metal components into their oxides. Before being used in hydrotreating, the catalysts are generally pre-sulfurized to convert the hydrogenated metals into their sulfides.
[004] After 2-3 years of service, hydrotreating catalysts will be sent for metal recovery or will undergo a regeneration and rejuvenation process with the aim of restoring most of their initial activity. Lower activity of a regenerated catalyst is due to metal sintering in the regeneration process or during use, resulting in low dispersion of the active phase. This, in turn, produces lower activity compared to the activity of the fresh catalyst.
[005] Thus, in the method of the present invention, most of the lost activity is restored by treating the catalyst with a solution containing an organic acid and a base to redistribute the metals after regeneration.
[006] In addition to the regeneration of hydrotreating catalysts, the present invention relates to similar processes applied to other hydroprocessing catalysts, such as isomerization and hydrocracking catalysts, and such resulting catalysts.
[007] Rejuvenation methods that use acids Petition 870250015802, dated 26 / 02 / 2025, page 18 / 36 3 / 10 organic acids, which are described in the literature, do not address the problem of loss on attrition (LOA, as measured according to ASTM D4058-96), which is a state of physical instability that occurs when the acid is placed in contact with the alumina vehicle of a hydrotreating catalyst. When regenerated, alumina-based catalysts are treated with pure organic acids, and a high LOA is observed due to corrosion / dissolution of the vehicle surface.
[008] US 7,956,000 B2 describes a process for activating a hydrotreating catalyst comprising a group VIB metal oxide and a group VIII metal oxide. The process comprises contacting the catalyst with an acid and an organic additive having a boiling point in the range of 80–500°C and a water solubility of at least 5 g per liter (20°C, atmospheric pressure), optionally followed by drying under such conditions that at least 50% of the additive is retained in the catalyst. The hydrotreating catalyst may be fresh or may be a used catalyst that has been regenerated.
[009] It has now been found that the process described in the reference cited above can be improved if the catalyst is activated with a combination of an organic acid and an alkaline additive.
[010] In this way, the present invention relates to a method for activating a fresh oxide catalyst or the catalytically active material of a spent catalyst comprising a refractory oxide support and one or more base metals drawn from the group comprising nickel, cobalt, molybdenum and tungsten, said method comprising the steps of: - optionally regenerate the catalyst, - adjust an aqueous activation solution, containing an organic acid, to a pH > 3 with an alkaline additive, - impregnate the regenerated catalyst with the pH-adjusted aqueous activation solution, and Petition 870250015802, dated 26 / 02 / 2025, page 19 / 36 4 / 10 - Heat treat the catalyst at a temperature of 120-450°C.
[011] The catalyst regeneration stage involves the removal of deposits, especially combustible deposits, for example, thermal oxidation in the presence of oxygen.
[012] The step of adjusting an aqueous activation solution, containing an organic acid, to a target pH value above 3 with an alkaline additive, can also be performed by adding an amount of an aqueous solution containing an organic acid and adding an amount of an alkaline additive in two or more steps, wherein the mixing of the amount of an aqueous solution containing an organic acid and the amount of an alkaline additive would result in a solution with pH > 3. If the catalyst or catalytically active material comes into contact with an aqueous solution containing an organic acid before coming into contact with an amount of alkaline or basic additive, the time and / or temperature must be limited to avoid damage to the support.
[013] Since a fresh catalyst does not need to be regenerated, the optional catalyst regeneration step is only included when the catalytic material is a used (i.e., spent) catalyst.
[014] The acid used in the aqueous activation solution preferably contains at least one hydroxyl group.
[015] The target pH value of the aqueous activation solution is preferably between 4 and 7.
[016] As for base metals, these are present in the following quantities: Ni, Co: 1-10% by weight and Mo, W: 5-30% by weight.
[017] The standard solution in the field of the invention has been the use of a single organic acid to obtain the desired activity recovery. This, however, often results in a substantial LOA.
[018] Adjusting the activation solution to pH > 3, of Petition 870250015802, dated 26 / 02 / 2025, page 20 / 36 Preferably 5 / 10, for pH 4 < pH < 7, the problem of catalyst vehicle dissolution is mitigated. This can be easily done in existing factory or installation settings, involving only minor changes to the already applied procedure.
[019] In the absence of pH adjustments, the originally acidic activation solution is aggressive towards alkaline alumina vehicles, which are commonly used in hydrotreating catalysts, and will cause the vehicles to dissolve. This dissolution causes a deterioration in the mechanical stability of the catalyst, resulting in dust formation and / or an increase in LOA.
[020] In the catalysts used that are industrially regenerated to be activated, according to the invention, coke and sulfur are burned in a controlled manner to form metal oxides.
[021] The catalyst vehicle may comprise conventional refractory oxides, for example, alumina, silica, silica-alumina, alumina with silica-alumina dispersed therein, silica-coated alumina, magnesia, zirconia, boron and titania, as well as mixtures of these oxides. As a rule, preference is given to a vehicle being alumina, silica-alumina, alumina with silica-alumina dispersed therein or silica-coated alumina. Special preference is given to alumina and alumina containing up to 10% by weight of silica. A vehicle containing a transition alumina, for example an eta, theta or gamma-alumina, is preferred within this group, wherein a gamma-alumina vehicle is more especially preferred.
[022] Basic inorganic additives for adjusting pH can be ammonia or selected from the group of inorganic metal salts of hydroxides, carbonates, bicarbonates, oxides and phosphates, for example, LiOH, KOH, NaOH, NH3, Ca(OH)2, Mg(OH)2 and basic compounds of Co, Ni and Mo, such as carbonates, hydroxides and hydroxycarbonates of Co and Ni, as well as ammonium molybdates, ammonium metatungstate. The addition of metal salts of the active metals has the benefit of increasing the activity of Petition 870250015802, dated 26 / 02 / 2025, page 21 / 36 6 / 10 catalyst and can also be carried out by adding other Co, Ni, Mo and W compounds, such as nitrates, in the same step or independently of the addition of acid and base.
[023] The catalyst pore volume (measured by mercury penetration, 140-degree contact angle, 480 dyn / cm surface tension) is not critical to the method according to the invention and will generally be in the range of 0.2-2 ml / g, preferably 0.4-1 ml / g. The specific surface area is also not critical to the method according to the invention, and will generally be in the range of 50-400 m² / g (as measured using the BET method). Preferably, the catalyst will have an average pore diameter in the range of 6-15 nm, as determined by mercury porosimetry, and at least 60 percent of the total pore volume will be in the range of ± 3 nm of the average pore diameter and below a pore radius of 250 Å (50 nm diameter).
[024] Catalyst drying can, for example, be carried out in air, under vacuum or in an inert gas. Generally, it is advantageous to use a drying temperature below 220°C, although a higher or lower temperature may be necessary to promote or prevent reactions during drying.
[025] In one embodiment, a basic additive is added to the starting material in a first step, optionally followed by drying under such conditions that at least 50 percent of the added additive remains in the catalyst. Then, the resulting material is brought into contact with a solution of an organic acid, optionally followed by drying under such conditions that at least 50 percent of the alkaline and / or organic acid additive remains in the catalyst.
[026] The advantage of incorporating the acid and the additive into the catalyst in separate steps is that the properties of the impregnation solutions can be adapted to meet the requirements of the acid and the additive. However, for efficiency reasons, it is preferable to bring the catalyst into contact with Petition 870250015802, dated 26 / 02 / 2025, page 22 / 36 7 / 10 starting with a single impregnation solution comprising both the acid and the additive, optionally followed by a drying / calcination step under such conditions that at least 50 percent of the additive remains in the catalyst.
[027] In the context of the invention, an organic acid is defined as a compound comprising at least one carboxylic group (COOH). The organic acid is preferably a carboxylic acid comprising at least one carboxyl group and 6 or fewer carbon atoms, including the carbon atoms in the carboxyl groups. Suitable acids include 2-hydroxyethanoic acid, 2-hydroxypropane-1,2,3-tricarboxylic acid, 2-hydroxybutanedioic acid, 2-hydroxypropionic acid, 3-hydroxypropionic acid, 2-, 3- and 4-hydroxybutanoic acid, 2-, 3-, 4-, 5- and 6-hydroxyhexanoic acid, 2,3-dihydroxybutanedioic acid, 2,3-dihydroxypropanoic acid, 2,3,4,5,6-pentahydroxyhexanoic acid and polylactic acid. In addition, organic acids with 4 or fewer carbon atoms are generally preferred.
[028] The boiling point of the acid is preferably in the range of 100-400°C, more preferably 150-350°C. The boiling point of the acid is balanced between, on the one hand, the desire for the acid to remain in the catalyst during the preparation process, including the drying step, and on the other hand, the need to remove the acid from the catalyst during the use of the catalyst or sulfidation. If the organic acid does not have a boiling point, but decomposes within the specified temperature range, the term boiling point is synonymous with the decomposition temperature.
[029] The heat-treated acid and hydrotreating catalyst containing the additive of the present invention may undergo a sulfide step before being used in the hydrotreating of food hydrocarbons, but – as explained before – this is not necessary. If it is decided to sulfide Petition 870250015802, dated 26 / 02 / 2025, page 23 / 36 8 / 10 the catalyst before use, this can be done in one of the ways known in the art.
[030] For example, it is possible to bring the catalyst into contact with inorganic or organic sulfur compounds, such as hydrogen sulfide, elemental sulfur or organic polysulfides, or to bring the catalyst sulfide into contact with a hydrocarbon food to which a sulfur compound has been added. As indicated above, the catalyst to be activated in the method, according to the invention, is a fresh hydrotreating catalyst or a used hydrotreating catalyst that has been subsequently regenerated.
[031] Suitable fresh oxide hydrotreating catalysts for use as starting material in the method of the present invention are known in the art. They can be obtained, for example, as follows. A carrier precursor is prepared, for example, in the case of alumina, in the form of an alumina hydrogel (boehmite). After being dried, for example, by spray drying, it is molded into particles, for example, by extrusion. Then, the molded particles are calcined at a temperature in the range of 400-850°C, resulting, in the case of alumina, in a carrier containing a transition alumina, for example, a gamma-, theta- or eta-alumina. Then, suitable amounts of precursors for the hydrogenation metals and other optional components, such as phosphorus, are deposited on the catalyst, for example, in the form of an aqueous solution.
[032] In the case of Group VI and Group VIII metals, the precursors may be ammonium molybdate, ammonium tungstenate, cobalt nitrate and / or nickel nitrate. Suitable precursors for phosphorus components include phosphoric acid and the various ammonium hydrogen phosphates. After an optional drying step at a temperature in the range of 25-200°C, the material Petition 870250015802, dated 26 / 02 / 2025, page 24 / 36 The resulting 9 / 10 is calcined at a temperature in the range of 350-750°C, in particular 425-600°C, to convert all precursors of metal components, and the other optional precursor components to form oxide components.
[033] The activation process of the present invention is also applicable to the catalyst, which was used in the hydrotreatment of food from hydrocarbons and subsequently regenerated.
[034] The regeneration step of the process, according to the invention, is carried out by contacting the used additive-based catalyst with an oxygen-containing gas under such conditions that, after regeneration, the carbon content of the catalyst is generally less than 3% by weight, preferably less than 2% by weight, more preferably less than 1% by weight. After regeneration, the sulfur content of the catalyst is generally less than 2% by weight, preferably less than 1% by weight. Before the regeneration step, the carbon content of the catalyst is generally greater than 5% by weight, typically between 5 and 25% by weight. The sulfur content of the catalyst before the regeneration step is generally greater than 5% by weight, typically between 5 and 20% by weight.
[035] It is preferable that the regeneration step in the presence of oxygen be carried out in two stages, namely, a first stage at a lower temperature and a second stage at a higher temperature. In the first stage at a lower temperature, the catalyst is brought into contact with an oxygen-containing gas at a temperature of 100-370°C, preferably 175-370°C. In the second stage at a higher temperature, the catalyst is brought into contact with an oxygen-containing gas at a temperature of 300-650°C, preferably 320-550°C, even more preferably 350-525°C. The temperature during the second stage is higher than the temperature of the first stage discussed above, preferably by at least 10°C, more preferably by at least 20°C. Determining appropriate temperature ranges Petition 870250015802, dated 26 / 02 / 2025, page 25 / 36 10 / 10 is well within the scope of someone skilled in the technique, considering the indications above.
[036] It is preferable that the catalyst be regenerated in a moving bed process, preferably – if applicable – with a bed thickness of 1-15 cm. In the context of this descriptive report, the term moving bed is intended to refer to all processes in which the catalyst is in motion relative to the unit, including boiled bed processes, fluidized processes, processes in which the catalyst is rotated through a unit, and all other processes in which the catalyst is in motion.
[037] The duration of the regeneration process including removal will depend on the properties of the catalyst and the exact way the process is carried out, but will generally be between 0.25 and 24 hours, preferably between 2 and 16 hours.
[038] The regenerated catalyst will be placed in contact with the acid and additive in the process, according to the invention, as described above.
[039] The invention is illustrated in more detail in the example below: Example
[040] Two cases are described: In both cases, an industrially regenerated TK-609 HyBRIMTM sample was used and the LOA of the starting material was 0.3% by weight.
[041] In the first case, the regenerated catalyst was treated with 5.5 M 2-hydroxyethanoic acid, pH 1.12, followed by drying at 190°C for 2 hours. This treatment resulted in a LOA of 8.7% by weight.
[042] In the second case, the regenerated catalyst was treated with 5.5 M 2-hydroxyethanoic acid and 4.6 M NH3, pH 4.86, followed by drying at 190°C for 2 hours. This treatment resulted in a LOA of only 0.4% by weight.
Claims
1. A method for activating a fresh oxide hydroprocessing catalyst or the catalytically active material of a spent hydroprocessing catalyst comprising an alumina, silica-alumina, alumina with silica-alumina dispersed thereon, or alumina coated with silica and one or more base metals drawn from the group comprising nickel, cobalt, molybdenum, and tungsten support, said method characterized in that it comprises the steps of: - optionally regenerating the catalyst, - providing one or more activation solutions containing an organic acid and an alkaline additive, in amounts equivalent to an aqueous activation solution with a target pH greater than 3, - impregnating the catalytically active material with one or more aqueous activation solution(s), and - thermally treating the catalyst at a temperature of 120-450°C.
2. Method according to claim 1, characterized in that the organic acid in the aqueous activation solution has 6 or fewer carbon atoms.
3. Method according to claim 1, characterized in that the aqueous activation solution also contains an organic acid with a hydroxyl group.
4. Method according to claim 1 or 2, characterized in that the pH of the aqueous activation solution is 4 < pH < 7.
5. A method according to any one of claims 1 to 3, characterized in that the catalyst is heat-treated at a temperature of 120-220°C.
6. Method, according to any one of claims 1 to 3, characterized in that the catalyst is heat-treated at a temperature of 350-450°C. Petition 870250015802, dated 26 / 02 / 2025, page 13 / 36 2 / 2 7. A method, according to any of the preceding claims, characterized in that the organic acid is selected from 2-hydroxyethanoic acid, 2-hydroxypropane-1,2,3-tricarboxylic acid, 2-hydroxybutanedioic acid, 2-hydroxypropionic acid, 3-hydroxypropionic acid, 2-, 3- and 4-hydroxybutanoic acid, 2-, 3-, 4-, 5- and 6-hydroxyhexanoic acid, 2,3-dihydroxybutanedioic acid, 2,3-dihydroxypropanoic acid, 2,3,4,5,6-pentahydroxyhexanoic acid and polylactic acid.
8. A method, according to any of the preceding claims, characterized in that the alkaline additive is inorganic.
9. Method according to claim 8, characterized in that the alkaline inorganic additive is ammonia.