Incorporation of boron into hydrogenation catalysts, the resulting catalyst, and its use.

Abstract

1. A method for producing a support and a supported catalyst, the method comprising: (a) combining a porous inorganic oxide catalyst support or support extrudate with an aqueous solution, dispersion, or suspension comprising: (i) a boron-containing source; and (ii) an organic compound or organic chelating agent selected from organic compounds containing at least two oxygen atoms and 2 to 10 carbon atoms; (b) calcining composition (a) to reduce its loss on ignition (LOI) volatile matter content to greater than 0 wt. % to less than about 5 wt. %; (c) impregnating the calcined composition with an aqueous composition comprising at least one each of Group VIB and Group VIIIB metal-containing sources; and (d) calcining to reduce its LOI volatile matter content to greater than 0 wt. % to less than about 30 wt. %; wherein the boron content of the supported catalyst is in the range of about 1 wt. % to about 13 wt. % BO, based on the total weight of the catalyst.

Description

[Background technology]

[0001] Boron has been identified as an effective accelerator in hydrogenation catalysts. However, alternative methods for introducing boron into such catalysts, i.e., support catalysts, have been described. Some studies have shown that activity can be obtained by adding boron to an alumina support through kneading or precipitation reactions during the alumina synthesis process, while others indicate that it is preferable to add boron to the catalyst by impregnating it with a catalytically active metal.

[0002] Typically, boron is introduced using boric acid (H3BO3) as the boron source, but other boron-containing compounds can also be used. While directly adding H3BO3 to the alumina batch tank during alumina synthesis is feasible, it is inefficient, difficult to meter and control, and results in a large amount of boron leaching from the resulting filtration cake. Alternative methods include adding boron further downstream in the alumina synthesis, either near the drying stage of the formed alumina or as part of it. Alternatively, H3BO3 may be added to a catalyst metal impregnation solution, then to the alumina, and subsequently dried. A specific limitation on the addition of boron during the initial drying of the formed alumina and in the subsequent mixing steps discussed above is the risk of macropore formation (pores larger than 1 micron), which is generally detrimental to catalytic activity. A further known option for adding boron to a supporting catalyst is through the use of pore volume impregnation (PVI), which involves contacting an alumina composition extruded with an impregnation solution, the impregnation solution typically containing a mixture of dissolved catalyst metal compounds and optionally chelates. H3BO3 can be added to these impregnation solutions.

[0003] The solubility of boron compounds is a significant limiting factor when using impregnation solutions. Boric acid exhibits low water solubility (2.52 g / 100 mL at 0°C, which increases to only 5.7 g / 100 mL at 25°C). Its solubility is further reduced in metal impregnation solutions typically used in hydrogenation processes, including distillate hydrotreating (DHT). Once its solubility limit is reached, the solution becomes unstable, the boric acid component precipitates, and this leads to a limitation on the concentration of B2O3 in the catalyst, for example, to less than 1% by weight. The present invention addresses this drawback of the prior art, among other things. [Overview of the Initiative]

[0004] In one embodiment, a method for producing a support catalyst, the method comprising: (a) combining a porous inorganic oxide catalyst support or support extruder with an aqueous solution, dispersion, or suspension comprising (i) a boron-containing source and (ii) an organic compound or organic chelating agent selected from organic compounds containing at least two oxygen atoms and 2 to 10 carbon atoms to form a support composition containing boron and an organic compound; optionally, extruding the composition to form an extruder; and (b) calcining or drying and calcining the composition or extruder formed in (a) to reduce its volatile substance content by ignition loss (Loss on A method comprising: (c) reducing to a level greater than 0% by weight and less than about 5% by weight as measured by Ignition (LOI); impregnating the calcined composition formed in (b) with a solution, dispersion, or suspension containing at least one group VIB metal-containing component or source and at least one group VIIIB metal-containing component or source; and (d) calcining or drying and calcining the composition formed according to the impregnation step (c) to reduce its volatile content to a level greater than 0% by weight and less than about 30% by weight as measured by loss on ignition (LOI), wherein (1) the amount of the boron-containing source is sufficient to form a supporting catalyst having a boron content in the range of about 1% by weight to about 13% by weight, expressed as boron oxide B2O3, and based on the total weight of the catalyst; and (2) the loss on ignition (LOI) is measured by subjecting a weighed sample to an oxygen-containing atmosphere for 1 hour at 1020°F (548.9°C) and measuring the weight loss of the sample.

[0005] In another embodiment, a supported hydrogenation catalyst comprises a porous inorganic oxide catalyst support or catalyst support, at least one group VIB metal component in oxide form, at least one group VIIIB metal component in oxide form, a boron-containing component in oxide form represented as B2O3, and optionally a phosphorus component in oxide form represented as P2O5, wherein (a) the boron oxide content is in the range of 1 to 13% by weight based on the total weight of the catalyst, and (b) if present, the phosphorus component content is at least 1% by weight based on the total weight of the catalyst, (1) the group VIB and VIIIB metal components, as well as the phosphorus and boron components, are supported on or in a support or carrier comprising alumina or silica in the form of a pill having an internal cross-section and an external surface, (2) the position traversing the internal cross-section of the pill is identified by the percentage of the distance along the centerline from a first edge of the pill cross-section referred to as the starting point or 0% to the furthest edge of the pill cross-section referred to as 100%, and (I) the first 33 (II) The concentration of group VIB metal oxides in 1 / 3% or the last 33 1 / 3% is approximately 20% to 100% higher than the concentration of group VIB metal oxides in the central 33 1 / 3% of the pill cross-section, and the concentrations of group VIB and group VIIIB metal oxide components, and if present, phosphorus oxide components, up to the outer surface across the cross-section of the pill are determined using electron probe trace analysis.

[0006] In more specific embodiments of the present invention disclosed herein, a process is provided for producing a supporting catalyst composition, the process comprising (optionally, "essentially consisting of") the features described above, and the product similarly comprising (optionally, "essentially consisting of") the features described above.

[0007] By implementing the present invention, one or more advantages, including the following, can be achieved: Improved catalytic activity: As demonstrated by performance tests and activity results using the supported catalyst prepared according to the present invention, the boron impregnation method claimed hereof yields excellent catalytic activity for both hydrodesulfurization (HDS) and hydrodenitrification (HDN). Specifically, the method for preparing the supported catalyst provides a means to obtain a significant improvement in catalytic activity with only a small increase in raw material or process costs.

[0008] Control of final catalyst pore size distribution (PSD): PSD is a critical parameter in controlling catalytic activity and stability. Depending on how boron is added to the supporting catalyst, the PSD can be fixed at, for example, smaller pore sizes and cannot be adjusted by using other process variables, such as changes in calcination temperature. This can result in a catalyst with lower activity. In contrast, by implementing the method of the present invention, it becomes possible to use any inorganic oxide support having any desired initial PSD suitable for the intended hydrogenation process. Notably, the addition of boron by the method of the present invention does not alter the pore structure, e.g., PSD, as can typically occur when using conventional kneading, mixing, and other equivalent techniques for introducing boron.

[0009] Control of Boron Concentration in Supports and Supporting Catalysts: Using the method of the present invention, the amount of boron introduced into supports and supporting catalysts can be precisely controlled. Specifically, a relatively large amount of boron can be impregnated into the support without concern for boron solubility around the support or macropore formation in the support. Therefore, the amount of boron can be scaled up or down relatively easily to optimize catalytic activity in a desired hydrogenation process.

[0010] Mitigation of the risk of macropore formation. Introducing boron by adding boric acid to inorganic support materials using indirect heat exchange with extrusion equipment and screw caps, or during mixing, granulation, and kneading processes, typically involves the formation of macropores (pores with a diameter greater than 1 micron). Macropore formation is considered detrimental and can reduce catalytic activity and stability, and is therefore undesirable.

[0011] Improved Flexibility: Generally, the processes of the present invention disclosed herein are readily modifiable by those skilled in the art. Various metal solutions and supports may be used instead of those exemplified herein.

[0012] Preservation of chelated metals during catalyst synthesis: As disclosed below, the claimed method typically uses a higher temperature and / or extended calcination time during the initial boron impregnation step, followed by less harsh drying and / or calcination conditions to produce a supporting catalyst, which enables the synthesis of a highly active chelated catalyst containing boron at a desired target level concentration. [Brief explanation of the drawing]

[0013] [Figure 1] This graph shows the pore size distribution of the support prepared according to the present invention, both during the first and second stages of preparation. [Figure 2] The images show representative EPMA scans of non-uniformly distributed elements in a cross-section of an asymmetrical four-leaf clover-shaped extruded prepared according to the present invention, and electron microscope images of the cross-section of the extruded identifying the longitudinal positions in the length direction measured using EPMA. [Figure 3] This graph shows the sulfur content in liquid hydrogenated diesel fuel products correlated with temperature, using the support catalyst and comparative support catalyst of the present invention. [Figure 4] The temperature and pressure test conditions for evaluating the HDS and HDN activity of the supporting catalyst are shown. [Figure 5] The baseline and HDS and HDN activities of the Mo / Co-supported catalyst of the present invention are shown under various test conditions. [Figure 6] Shows the HDS and HDN activities of the baseline and the Mo / Ni supported catalyst of the present invention under various test conditions. [Figure 7] Shows the pore size distribution of the variously prepared supported catalysts. [Figure 8] Shows the HDS and HDN activities of the variously prepared supported catalysts. [Figure 9] Shows the pore size distribution of the variously prepared supported catalysts. [Figure 10] Shows the HDS and HDN activities of the variously prepared supported catalysts. [Figure 11] Shows the pore size distribution of the supported catalyst prepared according to the present invention using an alternative carboxylic acid during the first stage of impregnation. [Figure 12] Shows the HDS activity of the supported catalyst prepared according to the present invention using an alternative carboxylic acid during the first stage of impregnation. [Figure 13] Shows the EPMA scanning results for phosphorus along the longitudinal cross-section of the variously prepared supported catalyst particles. [Figure 14] Shows the EPMA scanning results for cobalt along the longitudinal cross-section of the variously prepared supported catalyst particles. [Figure 15] Shows the EPMA scanning results for molybdenum along the longitudinal cross-section of the variously prepared supported catalyst particles. [Figure 16] Shows the EPMA scanning results for cobalt, molybdenum, and phosphorus along the longitudinal cross-section of the selected supported catalyst particles.

Mode for Carrying Out the Invention

[0014] Definition To more clearly define the terms and phrases used herein, the following definitions are provided. If any definition or usage provided by any document incorporated herein by reference conflicts with the definitions or usage provided herein, the definitions or usage provided herein shall prevail.

[0015] When the term “about” is used as a modifier to a variable, feature, or condition, or in conjunction with a variable, feature, or condition, it is intended to convey that the number, scope, features, and conditions disclosed herein are flexible, and that the implementation of the invention by a person skilled in the art using properties such as temperature, rate, time, concentration, amount, content, base spacing, pore diameter, pore volume, and surface area, which are outside the scope described or different from a single described value, will achieve the desired or multiple results described in this application, namely, the preparation of porous catalyst support particles having defined features, and their use in the preparation of active olefin polymerization catalysts, and olefin polymerization processes using such catalysts.

[0016] Terms such as "a," "an," and "the" are intended to include multiple options, e.g., at least one, unless otherwise specified. For example, the disclosure of "inorganic oxides," "VIB metals," or "boron sources" means that one or more mixtures or combinations are included.

[0017] The terms “catalyst” and “catalytic system” or “catalytic composition” are used interchangeably from time to time herein, and their use may be apparent from the context of this disclosure.

[0018] "Comprise" or "comprising": Throughout this Spec., including the claims, the words "comprising" and "comprises," as well as "have," "having," "includes," "include," and "including," and variations thereof, mean that the specified steps, elements, components, or materials referred to therein are essential, but other steps, elements, components, or materials may be added to still form a component within the scope of the claims or disclosure. Where described in the description of the invention and the claims, the invention and the claims are to be considered to be the following and potentially more. These terms are comprehensive or open-ended and do not exclude additional undescribed elements, components, or method steps, particularly when applied to the claims.

[0019] The term “contact product” is used herein to describe a composition in which components are in contact together in any order (unless a specific order is described or implied by the context of this disclosure), in any manner, and for any length of time. For example, components can be brought into contact by blending or mixing. Furthermore, contact of any component can occur in the presence or absence of any other component of the composition described herein, unless otherwise described or implied by the context of this disclosure. The addition of additional materials or components can be done by any preferred method. Furthermore, the term “contact product” includes mixtures, blends, solutions, slurries, reaction products, or combinations thereof. “Contact product” may include reaction products, but it is not required that the components react with each other. Similarly, the term “bring into contact” is used herein to refer to materials that can be brought into contact by blending, mixing, slurring, dissolving, reacting, processing, or any other manner.

[0020] EPMA or electron probe trace analysis uses approximately 100 mg / kg. -1 This is a test method (described further below) that combines the imaging capabilities of a focused electron beam with the analytical capabilities obtained by induced X-rays to produce spatial resolution analysis of a wide range of elements with a detection limit.

[0021] "Group" or "Multiple Groups": Any reference to a group or multiple groups in the periodic table is preferably a reference to a group or multiple groups reflected in the periodic table, identified by Roman numerals, according to the periodic table published in, for example, "Hawley's Condensed Chemical Dictionary" (Thirteenth edition, 1997) ("CAS version"). Alternatively, groups can be identified using the IUPAC system for numbering groups of elements as groups 1 through 18; see, for example, the periodic table published by the International Union of Pure and Applied Chemistry (IUPAC) and also shown in Hawley's publication cited above, published online at http: / / old.iupac.org / reports / periodic_table / as of February 19, 2010.

[0022] Loss on ignition (LOI) is a measure of total volatile matter present in a sample such as porous inorganic oxides, catalyst compositions supported on inorganic oxides, or such oxides impregnated with various additives, including precursors or intermediates of such catalysts. Volatile matter is considered to consist of, or essentially consists of, water and thermally and / or oxidatively decomposable or decomposed organic components or residues. For the purposes of this disclosure, the LOI test is performed by subjecting the sample to an oxygen-containing atmosphere at 1020°F (548.9°C) for 1 hour, thereby oxidizing, decomposing, or igniting organic matter and displacing most, though not all, residual water in the catalyst.

[0023] The "average pore diameter" (APD) of a support or supporting catalyst can be calculated based on the measured total pore volume (V) and measured total surface area of ​​the support or supporting catalyst, according to the equation APD = 4V / A, and the result is expressed in angstroms.

[0024] As used herein, “pore volume” or “total pore volume” means the cumulative volume in cc / g of all pores identifiable by either nitrogen desorption or mercury intrusion, also known as porosimetry. For catalyst supports or carrier particles, particularly alumina powder, the pore size distribution and pore volume can be calculated by referring to nitrogen desorption isotherms (assuming cylindrical pores) using the BET (or BET) technique described by S. Brunauer, P. Emmett, and E. Teller in the Journal of the American Chemical Society, 60, pp209-31.9 (1939), and also refer to ASTMD3037, which identifies the procedure for determining surface area using the nitrogen BET method.

[0025] The pore size distribution (PSD) is determined using ASTMD4284-07, "A Standard Test Method for Determining Pore Volume Distribution of Catalysts by Mercury Intrusion Porosimetry." This method is a generally accepted test used to determine the volume distribution of pores in catalysts and catalyst supports or support particles relative to the apparent diameter of the pore inlet. As discussed above, both the size and volume of pores in a catalyst generally affect its performance. Therefore, the pore volume distribution is useful for understanding catalytic performance and can be one of the characteristics identified for a catalyst that is expected to function in a desired manner. Various attributes of the pore volume distribution, including the total pore volume or total intrusion volume, as well as the percentage of pores in various size ranges, and pore modes, are based on the mercury intrusion method.

[0026] The pore size distribution is given by the following formula:

[0027]

number

[0028] The total N2 pore volume of the sample is the sum of the nitrogen pore volumes determined by the nitrogen desorption method described above. Similarly, the total mercury pore volume of the sample is the sum of the mercury pore volumes determined by the mercury intrusion method described above, using, for example, a contact angle of 130°, a surface tension of 485 dynes / cm, and an Hg density of 13.5335 gm / cc.

[0029] In this specification, "surface area" refers to the specific surface area determined by nitrogen adsorption using the BET technique described above, whether in powder or aggregate form.

[0030] Pore ​​volume, PV (cc / g), or surface area, (SA) (m²) 2 All morphological properties related to weight, such as ( / g), can be normalized to a "metal-free standard" according to procedures well known in the art. However, the morphological properties reported herein are "as measured" standards that have not been corrected for metal content.

[0031] "Substantially": Unless otherwise defined with respect to a specific characteristic, feature, or variable, the term "substantially" applied to any criterion such as a characteristic, feature, or variable means that the criterion described is met to such an extent that a person skilled in the art would understand that the benefit to be achieved, or the desired condition or characteristic value, is met. For example, see below for the use of the term "substantially" in relation to a description of a metallocene catalyst or catalytic system that substantially does not contain an aluminoxane or borate activator. Or, for example, the phrase "substantially does not contain" with respect to an aluminoxane or borate activator is used to convey the same concept, condition, or result. In other words, the scope of the term "substantially" is to describe the subject matter in a way that is understood by a person skilled in the art of the invention, and to appropriately serve to distinguish the claimed subject matter from the prior art.

[0032] The applicants reserve the right, if for any reason they choose to claim less than the entire scope of the disclosure, to exclude or omit any individual member of any such group (including any sub-scope or combination of sub-scopes within that group) which may be claimed in accordance with the scope or in any similar form, for example, the right to include references which the applicants may not have been aware of at the time of filing this application. Furthermore, the applicants reserve the right, if for any reason they choose to claim less than the entire scope of the disclosure, to exclude or omit any individual substituent, analogue, compound, ligand, structure, or any group thereof, or any member of the claimed group, for example, the right to include references which the applicants may not have been aware of at the time of filing this application. The applicants disclose several types of scopes in the present invention, including, but not limited to, ranges of weight ratios, ranges of molar amounts or molar ratios, and ranges of temperatures. When an applicant discloses or claims any type of scope, the applicant's intent is to individually disclose or claim each possible number that such scope may appropriately encompass, including the endpoints of the scope, and any sub-scopes and combinations of sub-scopes contained therein. For example, when an applicant discloses or claims a chemical part having a particular number of carbon atoms, the applicant's intent is to individually disclose or claim all possible numbers that such scope may encompass, consistent with the disclosures herein.

[0033] Porous carrier or support material Examples of suitable inorganic fine particle porous (or porous) carrier materials include silica, silica gel, silica-alumina, alumina, titania, titania-alumina, zirconia-alumina, zirconia, boria, terrana, kaolin, magnesium silicate, magnesium carbonate, magnesium oxide, aluminum oxide, precipitated aluminum oxide, activated alumina, bauxite, diatomaceous earth, pumice, natural clay, synthetic clay, saponite, bentonite, kaolin, sepiolite, or cationic or anionic clays such as hydrotalcite, and mixtures thereof. Preferred porous carrier components are silica, silica-alumina, alumina, titania, titania-alumina, zirconia, bentonite, boria, and mixtures thereof, with silica, silica-alumina, alumina, and mixtures thereof being particularly preferred. Alumina can be prepared, for example, from alumina precursors such as boehmite or pseudoboehmite.

[0034] When the porous inorganic oxide support is alumina or an alumina-containing composition, the crystalline form of the alumina will depend on the firing conditions used in the process, particularly the temperature, and the combination of time and temperature. For example, a firing temperature range of 400°C to 800°C typically produces gamma-alumina, a firing temperature of 800°C to 1150°C typically produces theta-alumina, and firing above 1150°C typically results in the formation of alpha-alumina. Of the above forms, gamma or theta-alumina are preferred, but alpha-alumina is less preferred because it typically contains a higher content of pores with diameters exceeding 1000 angstroms, unless such larger pores are more desirable for use in connection with a specific intended hydrogenation treatment or hydrogenation operation. It is also possible to obtain eta-alumina, chi-alumina, etc., by using other temperatures and times.

[0035] A typical method for preparing alumina-containing particles for use as a component of inorganic oxides or inorganic oxide-supported catalysts involves mixing uncalcined pseudo-boehmite alumina powder with water, or optionally, thoroughly mixing it with a diluted aqueous solution containing an inorganic acid such as nitric acid, or an organic acid such as acetic acid, or formic acid, and preferably by extrusion molding, forming the alumina mixture containing about 50-65 weight percent water into catalyst support particles of the desired size and shape.

[0036] Preferred shapes include powders, spherical, cylindrical, ring-shaped, and symmetrical or asymmetrical multi-lobed forms, such as tri-lobed and quadruple-lobed forms, which are generally referred to as "piles." Particles resulting from extrusion, beading, or pelletizing typically have a diameter in the range of about 0.2 to about 10 mm and a length in the range of about 0.5 to about 20 mm, although deviations from these general ranges are possible. Catalyst-supporting particles and supporting catalysts formed from extruded materials are generally preferred.

[0037] firing The process of the present invention typically comprises two independent calcination steps, which are described in detail below. Generally, calcination can be carried out in batch or continuously by bringing a molded carrier or support product, or an impregnated and molded carrier or support composition, into contact with a high-temperature gas, which may be either an indirectly heated gas or a combustion product of a normal fuel with air or heated air or an inert gas. Regardless of the specific method used, calcination is typically carried out at a temperature of about 538°C (1000°F) to about 1093°C (2000°F), or about 649°C (1200°F) to about 1038°C (1900°F), such as about 760°C (1400°F) to about 982°C (1800°F), for a period of about 30 minutes to about 3 hours, or about 45 minutes to about 2.5 hours, preferably about 30 minutes to about 2 hours. Alternatively, firing may be carried out at temperatures ranging from approximately 400°C to 1150°C, or approximately 500°C to 1000°C, or approximately 600°C to 800°C, or approximately 800°C to 1150°C. Preferably, firing temperatures are approximately 400°C, or approximately 450°C, or approximately 500°C, or approximately 550°C, or approximately 600°C, or approximately 650°C, or approximately 700°C, or approximately 750°C, or approximately 800°C to approximately 500°C, or approximately 550°C, or approximately 600°C, or approximately 650°C, or approximately 700°C, or approximately 750°C, or approximately 800°C, or approximately 850°C, or approximately 900°C, or approximately 900°C, or approximately 950°C, or approximately 1000°C, or approximately 1050°C, or approximately 1100°C, provided that each of the lower temperature limits listed is related to the upper temperature limit for creating a suitable firing temperature range.

[0038] The extruded inorganic oxide particles impregnated with boron and selected organic compounds from step 1 may, for example, be calcined at a temperature of about 400°C to about 750°C for about 1 to 2 hours, or, for example, be dried at a temperature of about 110°C to about 150°C and then calcined at a temperature of about 400°C to about 750°C for about 1 to 2 hours, provided that the calcined particles exhibit an LOI of more than 0% by weight and less than about 5% by weight. On the other hand, inorganic oxide particles comprising at least one metal from group VIB and at least one metal from group VIIB, optionally but preferably containing phosphorus, in other words, the composition produced in step 2, can be, for example, calcined at a temperature of about 400°C to about 750°C for about 1 to 2 hours, or, for example, dried at a temperature of about 110°C to about 150°C and then calcined at a temperature of about 400°C to about 750°C for about 1 to 2 hours, provided that the calcined particles exhibit an LOI of more than 0% by weight, preferably about 1% by weight, or about 2% by weight, or more than about 3% by weight and less than about 30% by weight, or less than about 20% by weight, or less than 15% by weight, or less than 7% by weight.

[0039] Specific temperature and time conditions selected in one or more firing steps to yield a desired level of "loss on ignition" (LOI) of the composition to be fired are readily verifiable by those skilled in the art using simple experiments including: (1) a molded porous support or body impregnated with boron and an organic compound selected from those described elsewhere herein (referred to as the first step); or (2) a molded porous support or body containing boron and an organic compound from (1), further impregnated with at least one group VIB and at least one group VIIIB catalyst metal, and optionally but preferably phosphorus (referred to as the second step). As disclosed elsewhere herein, the typical and preferred LOI values ​​and ranges of compositions (1) and (2) may differ from one another. Typically, the LOI of a composition produced in step (1) and subsequently fired will be less than the LOI of a composition produced in step (2) and subsequently fired. Therefore, the temperature and / or time firing conditions in step 1 will be more severe than the firing conditions used in step 2.

[0040] Therefore, any organic compound or organic chelating agent introduced with the boron source in the first stage will be substantially or completely decomposed and / or burned off as a result of the calcination conditions of the first stage. On the other hand, if the organic chelating agent is introduced together with one or more catalytically active metals in the second stage pore volume impregnation step, the less severe calcination conditions typically used in the second stage may allow for the retention of a portion of the organic chelating agent, or one or more complexes formed by the chelating agent and one or more catalytically active metals, or residues or decomposition products of the chelating agent or complex, or combinations of such components. For the sake of facilitating reference in this disclosure or claims, the presence of one or more such components in the supporting catalyst composition resulting from the second stage of the process of the present invention is simply referred to as “organic additives,” but may include complex organic-containing mixtures as described.

[0041] Suitable boron components, boron compounds, or boron sources for use in the present invention include inorganic and organic boron compounds. Such compounds include meta-boric acid (HBO2), orthoboric acid (H3BO3), hypoboric acid also known as tetrahydroxydiborone, ammonium borate tetrahydrate [(NH4)2B4O7.4H2O], sodium tetraborate, ammonium borate, ammonium tetraborate (NH4)2B4O7, boron oxide (B2O3), and various mono-, di-, and tri-alkylamines of borate, including, for example, triethanolamine borate, dimethylaminoborane, triethylborane, tributylborane, trimethyl borate, triethyl borate, and tricyclohexyl borate, and ammonium tetraphenylborate. Particularly preferred non-limiting examples of boron components include orthoboric acid (H3BO3), ammonium tetraborate tetrahydrate [(NH4)2B4O7.4H2O], and mixtures of two or more of the above.

[0042] The amount of boron in the catalyst is typically expressed as an oxide (B2O3) and will range from about 1 to about 13% by weight based on the total weight of the catalyst. In a preferred embodiment of the present invention, the amount of boron is expressed as an oxide (B2O3) and will range from about 1.5% to about 6% by weight based on the total weight of the catalyst. In another aspect of the present invention, the amount of boron is expressed as an oxide (B2O3) and will range from about 2% to about 5% by weight or about 4% to about 6% by weight based on the total weight of the catalyst. Therefore, expressed as oxide (B2O3) and based on the total weight of the catalyst, boron is approximately 1.0, 1.25, 1.5, 1.75, 2.0, 2.25, 2.5, 2.75, 3.0, 3.25, 3.5, 3.75, or approximately 4 wt% ~ expressed as oxide (B2O3) and based on the total weight of the catalyst, approximately 6 wt%, 6.25, 6.5, 6.75 , ranging from 7% by weight, 7.25% by weight, 7.5% by weight, 7.75% by weight, 8.0% by weight, 8.25% by weight, 8.5% by weight, 8.75% by weight, 9.0% by weight, 9.25% by weight, 9.5% by weight, 9.75% by weight, 10.0% by weight, 10.5% by weight, 11.0% by weight, 11.5% by weight, 12.0% by weight, 12.5% ​​by weight, or approximately 13.0% by weight.

[0043] In the implementation of the present invention, the phosphorus component or phosphorus source is optional, but when used, typically water-soluble acidic phosphorus compounds, particularly oxygenated inorganic phosphorus-containing acids, are typically preferred. Examples of suitable phosphorus compounds include metaphosphoric acid, pyrophosphoric acid, phosphorous acid, orthophosphoric acid, triphosphoric acid, tetraphosphoric acid, and precursors of phosphorus acids such as ammonium hydrogen phosphate (monoammonium dihydrogen phosphate, diammonium monohydrogen phosphate, triammonium phosphate). A mixture of two or more phosphorus compounds may be used. The phosphorus component or compound may be used in liquid or solid form. Preferred phosphorus compounds are preferably orthophosphoric acid (H3PO4) or ammonium hydrogen phosphate in aqueous solution.

[0044] The amount of phosphorus compound used in the catalyst may vary depending on the process in which the supporting catalyst will be used, and therefore, excluding phosphorus from the supporting catalyst composition, in other words, 0% by weight of P2O5, is within the scope of the present invention. However, if a phosphorus source (as oxide P2O5) is included, it will typically be sufficient to provide at least about 0.5% by weight based on the total weight of the catalyst. In other aspects of the present invention, it will be about 0.5% to about 5% by weight, or at least about 1% or about 2% by weight, based on the total weight of the catalyst. In yet another aspect of the present invention, the amount of phosphorus compound used (as oxide P2O5) will be sufficient to provide phosphorus in the range of about 4% to about 10% by weight based on the total weight of the catalyst. In yet another aspect of the present invention, the amount of phosphorus compound used (as oxide P2O5) will be sufficient to provide phosphorus in the range of about 4% to about 7% by weight based on the total weight of the catalyst. Therefore, phosphorus in the range of approximately 0, 0.25, 0.5, 0.75, 1.0, 1.25, 1.5, 1.75, 2.0, 2.25, 2.5, 2.75, 3.0, 3.25, 3.5, 3.75, or approximately 4% by weight to approximately 7% by weight, 7.25% by weight, 7.5% by weight, 7.75% by weight, 8.0% by weight, 8.25% by weight, 8.5% by weight, 8.75% by weight, 9.0% by weight, 9.25% by weight, 9.5% by weight, 9.75% by weight, 10.0% by weight, 10.5% by weight, 11.0% by weight, 11.5% by weight, 12.0% by weight, 12.5% ​​by weight, or approximately 13.0% by weight.

[0045] Suitable catalytically active elements or metals from Group VIIIB of the periodic table present in the components of the present invention include Fe, Co, Ni, Pd, Pt, Rh, Ru, and mixtures thereof. Of these, the most preferred are Co, Ni, and Pt. Suitable Group VIB elements or metals include Cr, Mo, W, and mixtures thereof, with the most preferred being Mo and W. Typically, the supporting catalyst contains about 5 to about 40% by weight of Group VIB metal oxides, such as MoO3 and / or WO3, or about 6 to about 35% by weight, or about 7 to about 30% by weight, or about 8 to about 25% by weight. Also typically, the supporting catalyst contains about 1 to about 20% by weight of Group VIB metal oxides, such as CoO and / or NiO, or about 2 to about 18% by weight, or about 3 to about 16% by weight, or about 4 to about 14% by weight. Preferred combinations of metal components include, for example, nickel and molybdenum, cobalt and molybdenum, tungsten and nickel or cobalt, combinations of molybdenum, cobalt and nickel, combinations of tungsten, nickel and cobalt, and combinations of molybdenum, chromium and nickel, with the combination of molybdenum and nickel and / or cobalt being particularly preferred. For each of the metal combinations described above, phosphorus is an optional but preferred component. The amounts of group VIB and group VIIIB metals can be determined using standard, well-known analytical methods such as atomic absorption spectrometry (AAS), inductively-coupled plasma spectrometer (ICP) analysis, and / or X-ray fluorescence (XRF).

[0046] A suitable process for preparing a stable impregnation solution can be described as follows: The preparation of catalytically active metal solutions or dispersions for pore volume impregnation in the second stage of impregnation is well known to those skilled in the art, and should be seen, for example, U.S. Patents 7,390,766, 7,560,407, and 7,642,212, which are incorporated herein by reference to the extent permitted. Exemplary useful preparation methods are described in the following paragraphs.

[0047] A slurry is formed by adding a certain amount of substantially water-insoluble group VIIIB metal component to water. The amount of group VIIIB metal component is small compared to the amount of group VIB metal component that will be added in subsequent steps. The specific amount of substantially water-insoluble group VIIIB metal component can be characterized by the molar ratio of group VIIIB metal to group VIB metal in the final impregnation solution, which is typically about 0.05 to about 0.75, and other preferred ranges for this variable and other variables are described below.

[0048] In catalyst compositions optionally but preferably containing a phosphorus component, an aqueous solution of a water-soluble phosphorus-containing acidic component is added to the aqueous slurry of the substantially water-insoluble Group VIIIB metal component described above. The amount of the acidic phosphorus component is small compared to the amount of Group VIB metal component that will be added in subsequent steps, and this level may be insufficient to make the Group VIIIB metal component substantially soluble at this stage of the process, but the components added in those steps described above are expected to react. Typically, a slurry of components is obtained at this stage. The specific amount of the water-soluble phosphorus-containing acidic component can be characterized by the molar ratio of elemental phosphorus to Group VIB metal in the final impregnation solution, which is typically about 0.01 to about 0.80. The concentration of the Group VIB metal component in the impregnation solution composition can be very high, up to about 50 weight percent, expressed as an oxide and based on the total weight of the impregnation solution composition. It will be apparent to those skilled in the art that by diluting the concentrated composition with a suitable amount of water, more dilute solutions useful for specific applications can be obtained.

[0049] Additional group VIIIB metals in the form of substantially water-soluble group VIIIB metal components can be added to the following composition as needed to obtain desired levels of group VIIIB metal components and desired ratios of group VIIIB metal components to group VIB metal components in the resulting catalyst. Thus, the molar ratio of group VIIIB metal components to group VIB metal components can vary from about 0.05 to about 1.0. The catalyst-impregnated composition produced by the described method allows for a high concentration of group VIB metal components and low relative concentrations of both phosphorus and group VIIIB metal components. The low relative concentration of phosphorus components may be advantageous for the preparation of catalysts that can benefit from or tolerate low levels of phosphorus. In addition, the resulting catalyst-impregnated solution is remarkably stable, i.e., it can be stored as a solution for long periods without forming precipitate species.

[0050] A low relative concentration of the group VIIIB metal component may be advantageous. Firstly, such compositions allow for the preparation of catalysts in a wide range of ratios of group VIIIB to group VIB metal components. Secondly, a substantial amount of the group VIIIB metal component required for the finished catalyst can be added in the form of a substantially water-soluble group VIIIB metal component; otherwise, this group VIIIB metal component may be difficult to solubilize in the presence of a large amount of group VIB metal component unless a significantly large amount of acidic phosphorus component is used. A substantially water-soluble group VIIIB metal component, especially a salt of a mineral acid (e.g., nitrate), may be more cost-effective than a substantially water-insoluble salt of the group VIIIB metal component (e.g., carbonate). Thirdly, controlled heating of the impregnated catalyst at a high temperature but without calcination, or calcination at a temperature lower than a typical calcination temperature, can facilitate the removal of water from the catalyst, thus reducing the adverse effects of excess water during startup when the catalyst is used in a hydrogenation treatment or hydrogenation conversion operation, while maintaining an effective amount of chelating agent or chelating metal complex. Alternatively, controlled heating and calcination can be used to achieve the desired level of LOI in the intermediate or final supporting catalyst composition.

[0051] Suitable Group VIIIB metal components for use in the present invention, characterized herein as substantially water-insoluble, include citrates, oxalates, carbonates, hydroxycarbonates, hydroxides, phosphates, phosphides, sulfides, aluminates, molybdates, tungstates, oxides, or mixtures thereof. Oxalates, citrates, carbonates, hydroxycarbonates, hydroxides, phosphates, molybdates, tungstates, oxides, or mixtures thereof are preferred, with hydroxycarbonates and carbonates being the most preferred. Generally, the molar ratio of hydroxyl groups to carbonate bases in hydroxycarbonates is in the range of about 0 to 4, preferably about 0 to 2, more preferably about 0 to 1, and most preferably about 0.1 to 0.8. In particular, suitable substantially water-insoluble components for providing Group VIIIB metals are nickel and cobalt oxides, carbonates, and hydroxides.

[0052] Suitable substantially water-soluble components for providing Group VIIIB metals for use in the present invention include salts such as nitrates, hydrated nitrates, chlorides, hydrated chlorides, sulfates, hydrated sulfates, formates, acetates, or hypophosphates. Suitable substantially water-soluble nickel and cobalt components include nickel nitrate, nickel sulfate, nickel acetate, nickel chloride, nickel formate, or mixtures thereof, as well as nickel hypophosphite. Suitable water-soluble iron components include iron acetate, iron chloride, iron formate, iron nitrate, iron sulfate, or mixtures thereof. In particular, substantially water-soluble components are salts such as nitrates, sulfates, and acetates of nickel and cobalt.

[0053] An indicator of the relative solubility of substantially insoluble and soluble components can be found, for example, by comparing nickel carbonate with nickel nitrate or nickel sulfate. (CRC Handbook of Chemistry and Physics, 69) thAs reported in Ed., 1988-9 (RCWeast, Ed., CRC Press), nickel carbonate has a water solubility of approximately 0.009 g / 100 mL, nickel nitrate has a solubility of approximately 239 g / 100 mL, and nickel sulfate has a solubility of approximately 29–76 g / 100 mL depending on the water of hydration of the particular salt. Furthermore, the solubility of sulfates increases to approximately 87–476 g / 100 mL in hot water. Consequently, those skilled in the art will understand the reference to "substantially" regarding the water solubility of these components. Alternatively, for the purposes of the present invention, the water solubility of substantially water-insoluble Group VIIIB metal components is generally less than 0.05 mol / 100 mL (at 18°C), while the solubility of substantially water-soluble components is greater than 0.05 mol / 100 mL, for example, about 0.10 mol / 100 mL (at 18°C).

[0054] Suitable components for providing VIB group metals include both substantially water-soluble and substantially water-insoluble components. Suitable substantially water-soluble VIB group metal components include monomolybdic acid and ammonium tungstate or alkali metals, as well as water-soluble isopolycompounds of molybdenum and tungsten such as metatungstic acid and metatungstate, or VIB group metal salts such as water-soluble heteropolycompounds of molybdenum or tungsten containing, for example, P, Si, Ni, or Co, or combinations thereof. Suitable substantially water-soluble isopoly and heteropolycompounds are described in Molybdenum Chemicals, Chemical data series, Bulletin Cdb-14, February 1969 and Molybdenum Chemicals, Chemical data series, Bulletin Cdb-12a-revised, November 1969. Suitable substantially water-soluble chromium compounds include chromates, isopolychromates, and ammonium chromium sulfate. Suitable VIB group metal components that are substantially water-insoluble, for example, have low water solubility, include di and trioxides, carbides, nitrides, aluminum salts, acids, sulfides, or mixtures thereof. Preferred substantially water-insoluble VIB group metal components are di and trioxides, acids, and mixtures thereof. Suitable molybdenum components include molybdenum di and trioxides, molybdenum sulfide, molybdenum carbide, molybdenum nitride, aluminum molybdate, molybdic acid (e.g., H2M OExamples include ammonium phosphomolybdate, ammonium di and heptamolybdate, or mixtures thereof, with molybdic acid and molybdenum di and trioxide being preferred. Suitable substantially insoluble tungsten components include tungsten di and trioxide, tungsten sulfide (WS2 and WS3), tungsten carbide, orthotungstic acid (H2WO4·H2O), tungsten nitride, aluminum tungstate (also meta or polytungstate), ammonium phosphotungstate, or mixtures thereof, with ammonium metatungstate, ammonium orthotungstate, and tungsten di and trioxide being preferred. Most preferred is molybdenum trioxide, M O The solution is O3. For the purposes of the present invention, the water solubility of substantially water-insoluble VIB metal components is generally less than 0.05 mol / 100 mL (at 18°C), while the solubility of substantially water-soluble components is greater than 0.05 mol / 100 mL, for example, about 0.10 mol / 100 mL. Other suitable metal salts can be readily determined by referring to the references listed above or other suitable references available to those skilled in the art.

[0055] If present, the phosphorus-containing acidic component is substantially water-soluble and preferably a water-soluble acidic component that may be an oxygenated inorganic phosphorus-containing acid such as phosphoric acid, but any one or more phosphoric acids including orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid, and mixtures thereof, can be used. For the purposes of the present invention, substantially water-soluble phosphorus means solubility sufficient to react with substantially water-insoluble Group VIII metal components. In addition, soluble salts of phosphoric acid, such as ammonium phosphate, can also be used. Phosphoric acid can be added to the solution in liquid or solid form. The preferred compound is orthophosphoric acid (H3PO4) in a highly concentrated aqueous solution, but any suitable form of phosphoric acid or its precursor, such as phosphorus pentoxide (P2O5), can be used. Of course, a concentrated acid may be used after being appropriately diluted, or a suitable form of dilute acid may be used directly.

[0056] Suitable compounds or chelating agents include organic additives such as (i) organic compounds selected from the group consisting of compounds containing at least two oxygen atoms and 2 to 10 carbon atoms, and compounds composed of or derived from these compounds, or (ii) organic compounds containing at least one covalently bonded nitrogen atom and at least one carbonyl moiety, or both of (i) and (ii). The organic compounds according to (i) above are preferably selected from the group consisting of compounds containing at least two oxygen-containing moieties such as carboxyl, carbonyl, or hydroxyl moieties and 2 to 10 carbon atoms, and compounds composed of or derived from these compounds. Compounds composed of or derived from organic compounds may be, for example, ethers, esters, acetals, acid chlorides, acid amides, oligomers, or polymers of organic compounds. Examples of suitable organic compounds include carboxylic acids such as citric acid, tartaric acid, oxalic acid, malonic acid, maleic acid, and malic acid; as well as butanediol, pyruvate aldehyde, glycolaldehyde, and acetaldol. More preferably, the organic compounds are selected from the group consisting of compounds containing at least two hydroxyl groups and 2 to 10 carbon atoms per molecule, and compounds composed of these compounds. Examples of preferred compounds include tartaric acid, or aliphatic alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolethane, and trimethylolpropane. Examples of compounds composed of these organic compounds include oligomers and polymers, such as diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, and tetrapentylene glycol. This range can be extrapolated to include polyethers, such as polyethylene glycol. With respect to polyethylene glycol, polyethylene glycol having a molecular weight of 200 to 8,000 is preferred.Other compounds composed of these organic compounds include ethers such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether. Preferred organic compounds are, in particular, ethylene glycol, diethylene glycol, polyethylene glycol, or mixtures thereof. Another group of organic compounds containing at least two hydroxyl groups and 2 to 10 carbon atoms per molecule are formed by monosaccharides such as glucose and fructose. Compounds composed of these organic compounds include oligomers and polymers, disaccharides such as lactose, maltose, and saccharose, and polysaccharides.

[0057] The organic compound according to (ii) preferably contains at least two carbonyl moieties. It is preferable that at least one carbonyl moiety is present on the carboxyl group. It is even more preferable that at least one nitrogen atom is covalently bonded to at least two carbon atoms. Preferred organic compounds satisfy formula (I) or (II), (R1R2)N-R3-N(R1'R2') (I) N(R1R2R1') (II) In the formula, R1, R2, R1', and R2' are independently selected from alkyl, alkenyl, and allyl groups having up to 10 carbon atoms, optionally substituted with one or more groups selected from carbonyl, carboxyl, ester, ether, amino, or amide. R3 is an alkylene group having up to 10 carbon atoms, which can be interrupted by -O- or -NR4-. R4 is selected from the same groups as those shown above for R1. The R3 alkylene group may be substituted with one or more groups selected from carbonyl, carboxyl, ester, ether, amino, or amide. As stated above, it is essential that the organic compound of formula (I) or (II) contains at least one carbonyl moiety. Preferably, at least two of R1, R2, R1', and R2' (formula (I)) and at least two of R1, R2, and R1' (formula (II)) have the formula -R5-COOX, where R5 is an alkylene group having 1 to 4 carbon atoms, and X is hydrogen, or another cation such as ammonium, sodium, potassium, and / or lithium cations. If X is a polyvalent cation, one X may be bonded to two or more -R5-COO groups. Typical examples of compounds of formula (I) are ethylene diamine(tetra)acetic acid (EDTA), hydroxyethylenediaminetriacetic acid, and diethylenetriaminepentaacetic acid. A typical example of a compound of formula (II) is nitrilotriacetic acid (NTA).

[0058] One criterion for establishing that a suitable intermediate composition after the first stage impregnation and calcination, or a supporting catalyst after the second stage impregnation and calcination, has been obtained, is to measure the weight percentage of the loss on ignition (LOI) of the composition or supporting catalyst. LOI is a measure of the total volatile matter or components present in the sample that can volatilize at high temperatures. These components mainly include water, but may also include residues or complexes of organic additives introduced during the first stage impregnation and / or organic chelating agents in the second stage impregnation. The LOI test is performed by exposing the sample to an oxygen-containing atmosphere at 1020°F (548.9°C) for 1 hour, thereby decomposing, oxidizing, or igniting organic matter and removing residual moisture to a degree considered suitable for the stages discussed herein. However, the temperature of the LOI test is not considered to be sufficiently high to significantly or adversely affect present inorganic oxide components, such as inorganic oxide supports and / or metal oxides or phosphorus oxide. This is because it is expected that the organic compounds present in the PVI impregnation solution will oxidize and / or volatilize to some extent, but the loss will target a specific final LOI level depending on the final use of the resulting supporting catalyst.

[0059] The composition obtained after the first calcination stage, and the composition obtained after the second calcination stage, or the supporting catalyst, prepared according to the present invention, have the following LOI values.

[0060] [Table 1]

[0061] The final supporting catalyst will typically exhibit an LOI of less than about 30% by weight, targeting about 20% by weight, preferably less than about 15% by weight, more preferably less than 14% by weight, for example, about 2% to about 15% by weight, or about 3% to about 7% by weight.

[0062] Furthermore, the LOI value exhibited after the second stage of calcination may be influenced by the type and amount of specific organic components or chelating agents contained in the PVI solution, as well as the level of moisture present in the composition at the time of impregnation, calcination, and thereafter. As a result, LOI levels in the supported catalyst after the second stage of calcination, summarized in Table 1 above, for example, greater than 0, or about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15% by weight to about 20 or about 30% by weight, can be achieved using the method of the present invention. Alternatively, approximately 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15% by weight to approximately 20% by weight, or approximately 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14% by weight to approximately 15% by weight, or approximately 3, 4, 5, or 6% by weight to approximately 7, 8, 9, or 10% by weight. Overall, whatever LOI level is achieved, it is expected that the desired amount of chelating agent, chelating agent residue, or chelated metal complex in the supporting catalyst composition will not be significantly and unfavorably reduced through either decomposition and / or volatilization as a result of the heating and calcination steps, but rather that a significant amount of residual water present in the wet supporting catalyst after the second-stage impregnation will be displaced or volatilized, or at least most of it.

[0063] Hydrocarbon conversion process The catalyst according to the present invention is particularly useful in a hydrogen-based hydrocarbon conversion process, which involves contacting a hydrocarbon feedstock with a particulate-supported catalyst under high temperature and high pressure conditions, and the catalyst is prepared according to the present invention. As generally described, such a catalyst comprises at least one catalytically active metal from Group VIB of the periodic table, at least one catalytically active metal from Group VIIIB of the periodic table, and optionally but preferably phosphorus, and a chelating agent, chelating agent residue, or chelated metal complex, wherein the metal, phosphorus, and chelating agent, chelating agent residue, or chelated metal complex are supported on a porous carrier, and the catalyst exhibits the controlled moisture level as described above.

[0064] The supporting catalyst prepared according to the present invention can be used under a wide range of reaction conditions, generally, for example, about 200°C.0 Temperatures in the range of approximately 500°C, hydrogen pressures in the range of approximately 5 to 300 bar, and approximately 0.05 to 10 hours. -1 The term "hydrogenation" can be used in virtually all hydrogenation processes for processing multiple feeds under liquid hourly space velocity (LHSV) in the range of . The term "hydrogenation" can encompass a variety of processes that react hydrocarbon feeds with hydrogen at high temperature and pressure (hydrogenation reaction conditions), including hydrogenation, hydrodesulfurization, hydrodenitrification, hydrodemetallation, hydrodesaromatherapy, hydroisomerization, hydrodewaxing, hydrocracking, and hydrocracking under mild pressure conditions, also known as mild hydrocracking.

[0065] More specifically, “hydrogenation,” as used herein, means a petroleum refining process in which petroleum feedstock (complex hydrocarbon mixtures) are reacted with hydrogen under pressure in the presence of a catalyst to reduce (a) the concentration of at least one of sulfur, contaminating metals, nitrogen, aromatic compounds, and Conradson residual carbon present in the feedstock, and (b) at least one of the viscosity, pour point, and density of the feedstock. In addition, the resulting oil color can be improved. Examples of hydrogenation include hydrocracking, isomerization / dewaxing, hydrogenation finishing, and hydrogenation processes that differ in the amount of hydrogen reacted and the properties of the petroleum feedstock being treated.

[0066] Hydrogenation is typically understood to involve the hydrogenation of a primarily hydrocarbon compound containing at least five carbon atoms per molecule ("feeding material") for the desulfurization and / or denitrification of said feeding material, wherein the process is carried out using (a) a partial pressure of hydrogen at superatmospheric pressure, (b) a temperature typically below 593.3°C (1100°F), (c) an overall net chemical consumption of hydrogen, and (d) in the presence of a solid-supported catalyst containing at least one hydrogenation component.

[0067] Hydrogenation finishing is typically understood to involve the hydrogenation treatment of hydrocarbon oils that primarily (by weight) contain hydrocarbon compounds ("feedings") within the lubricating oil boiling point range, and involves contacting the feedings with a solid-supported catalyst under high pressure and high temperature conditions, with the aim of saturating aromatic and olefin compounds, removing nitrogen, sulfur, and oxygen compounds present in the feedings, and improving the color, odor, heat, oxidation, and UV stability properties of the feedings.

[0068] Hydrocracking is typically understood to involve the hydrogenation of a primarily hydrocarbon compound ("feeding") containing at least five(5) carbon atoms per molecule, wherein the process is carried out using (a) a partial pressure of hydrogen at superatmospheric pressure, (b) a temperature typically below 593.3°C (1100°F), (c) an overall net chemical consumption of hydrogen, (d) in the presence of a solid-supported catalyst containing at least one(1) hydrogenation component, and (e) the feeding typically produces hydrocarbons in a yield of more than about 130(130) moles, each 100(100) moles of feeding containing at least about three(3) carbon atoms per molecule.

[0069] As is well known, these feedstocks contain nickel, vanadium, and asphaltene, for example, with a total combined amount of nickel and vanadium ranging from about 40 ppm to over 1,000 ppm, and asphaltenes up to about 25% by weight. Furthermore, the economics of these processes preferably produce lighter products and demetallated residual byproducts. This process is particularly useful for processing feedstocks containing a considerable amount of metal, having nickel and vanadium at a concentration of 150 ppm or more and a sulfur content ranging from about 1% by weight to about 10% by weight. Typical feedstocks that can be satisfactorily processed by the processes of the present invention contain a considerable amount (e.g., about 90%) of components that boil well above 537.8°C (1,000°F). Examples of typical feedstocks include crude oil, bald crude oil, petroleum hydrocarbon residues, both atmospheric and vacuum residues, oils obtained from tar sands, and residues derived from tar sands oil, as well as hydrocarbon flows derived from coal. Such hydrocarbon streams contain organometallic contaminants that have adverse effects in various purification processes that use catalysts in the transformation of the specific hydrocarbon stream being treated. Examples of metal contaminants found in such feedstocks include, but are not limited to, iron, vanadium, and nickel.

[0070] While metal contaminants such as vanadium, nickel, and iron are often present in various hydrocarbon streams, other metals are also present in certain hydrocarbon streams. Such metals exist as oxides or sulfides of certain metals, as soluble salts of certain metals, or as high molecular weight organometallic compounds including metal naphthenates and metal porphyrins, and their derivatives.

[0071] Another characteristic phenomenon in the hydrotreating of heavy hydrocarbons is the precipitation of insoluble carbonaceous materials or sediments from the asphaltene fraction of the feedstock, which cause operating problems. The sediments can accumulate on and inside various components downstream of the hydrotreating unit's equipment, interfering with the proper functioning of pumps, heat exchangers, fractionation towers, etc. The generation of excessive amounts of sediments is undesirable in that deposition in downstream units typically requires shutting down the equipment to remove the sediments. The amount of such sediments or insolubles formed increases with the amount of material being converted that boils above 537.8 °C (1,000 °F) or with an increase in the reaction temperature used. These insoluble materials, also known as Shell hot filtration solids, cause difficulties in the operation of the hydroconversion unit, thereby limiting the temperature and feed that the unit can handle. In other words, the amount of solids formed limits the conversion rate of a given feedstock. Such operating difficulties can begin to manifest at low solid levels of about 0.1 wt%. Levels below 0.5 wt% are generally desirable to prevent fouling of the process equipment. A description of the Shell hot filtration test is found in Van Kerkvoort, W.J. and Nieuwstad, A.J.J., A.J.J., Journal of the Inst, of Petroleum (1951) 37, pp. 596 - 604, which is incorporated herein by reference. Another useful test method for determining total sediment is described in ASTM D4870 - 92.

[0072] Operating conditions for the hydrotreating of heavy hydrocarbon streams such as petroleum hydrocarbon residues are well known in the art and include pressures in the range of about 1,000 psia (68 atm) to about 3,000 psia (204 atm), average catalyst bed temperatures in the range of about 700 °F (371 °C) to about 850 °F (454 °C), liquid hourly space velocities (LHSV) in the range of about 0.1 to about 5 hydrocarbon volumes per hour per volume of catalyst, and standard cubic feet per barrel (SCFB) of about 2,000 (356 m 3 / m 3) ~ approximately 15,000 SCFB (2,671m 3 / m 3 This includes a hydrogen recirculation rate or hydrogenation rate within the range of ). Preferably, the operating conditions include a total pressure in the range of about 1,200 psia to about 2,000 psia (81 to 136 atm), an average catalyst bed temperature in the range of about 730°F (387°C) to about 820°F (437°C), an LHSV in the range of about 0.1 to about 4.0, and about 5,000 SCFB (890 m 3 / m 3 ) ~ approximately 10,000 SCFB (1,781m 3 / m 3 This includes a hydrogen recirculation rate or hydrogenation rate within the range of ). Generally, the process temperature and space velocity are selected such that at least 30 vol% of the feed fraction boiling above 1,000°F is converted to a product boiling below 1,000°F, more preferably at least 50 vol% is converted to a product boiling below 1,000°F, and even more preferably at least 70 vol% of the target fraction is converted to a product boiling below 1,000°F.

[0073] In the treatment of hydrocarbon distillates, the operating conditions are typically a hydrogen partial pressure in the range of approximately 200 psia (13 atm) to approximately 3,000 psia (204 atm), an average catalyst bed temperature in the range of approximately 600°F (315°C) to approximately 800°F (426°C), and an LHSV of approximately 1,000 SCFB (178 m³) in the range of approximately 0.4 to approximately 6 volumes of hydrocarbon volume per hour of catalyst. 3 / m 3 ) ~ approximately 10,000 SCFB (1,381m 3 / m 3 This would include a hydrocarbon recirculation rate or hydrogenation rate within the range of ). Preferred operating conditions for the hydrogenation of hydrocarbon distillates would include a hydrogen partial pressure in the range of about 200 psia (13 atm) to about 1,200 psia (81 atm), an average catalyst bed temperature in the range of about 600°F (315°C) to about 750°F (398°C), an LHSV in the range of about 0.5 hydrocarbon volumes per hour per catalyst to about 4 hydrocarbon volumes per hour per catalyst, and about 1,000 SCFB (178 m 3 / m 3) ~ approximately 6,000 SCFB (1,068 m 3 / m 3 This includes hydrogen recirculation rates or hydrogen addition rates within the range of ).

[0074] Optionally, the supporting catalyst of the present invention may be sulfurized, sulfurized, or subjected to a sulfidation treatment to convert components of the supporting catalyst, particularly metal components, into their sulfides. In the context of this disclosure, the terms “sulfurizing” and “sulfidation” include any process steps or a set of steps in which a sulfur-containing compound or composition is brought into contact with the supporting catalyst, and at least a portion of the metal components present on or in the catalyst are converted into sulfide forms, either directly or as a result of activation or reaction in the presence of hydrogen. Suitable sulfidation processes are well known in the art. Sulfidation may be carried out in-situ, in-situ, or in combination of in-situ and in-situ steps or processes for one or more reactors in which the supporting catalyst is used to hydrogenate a hydrocarbon feedstock.

[0075] Out-of-situ sulfurization processes typically take place outside the reactor where a supporting catalyst is used to hydrogenate the hydrocarbon feed. In such processes, the supporting catalyst is brought into contact with a sulfur-containing composition and / or one or more sulfur compounds, such as polysulfides or elemental sulfur, outside the reactor and dried if necessary. In a typical second step, the initially treated supporting catalyst is optionally further treated with high-temperature hydrogen gas inside the reactor in the presence of the hydrocarbon feed to activate the catalyst, in other words, to bring the supporting catalyst into a sulfurized state.

[0076] On the other hand, the in-situ sulfidation process takes place in a reactor where a supporting catalyst is used to hydrogenate the hydrocarbon feedstock. In this process, the supporting catalyst is brought into contact with a stream of hydrogen gas mixed with a sulfidating agent such as hydrogen sulfide, or with a compound that can decompose to hydrogen sulfide under typical reaction conditions, such as dimethyl disulfide, in a high-temperature reactor. Alternatively, the hydrogen gas stream may be brought into contact with or combined with a hydrocarbon feedstock containing sulfur compounds that can decompose to hydrogen sulfide under typical conditions. In the latter case, sulfidation can be achieved by bringing the supporting catalyst into contact with a hydrocarbon feedstock containing added sulfidating agents (referred to as a spiked hydrocarbon feedstock), and it is also possible to use a sulfur-containing hydrocarbon feedstock without adding sulfidating agents, as sulfur components typically present in the feedstock are converted to hydrogen sulfide in the presence of the supporting catalyst. Various combinations of sulfidation techniques can also be applied. The use of a spiked hydrocarbon feedstock may be preferred in some cases.

[0077] Overview of the method for preparing the supporting catalyst The method of the present invention comprises an impregnation step comprising two main steps. In a preliminary process, an inorganic oxide suitable for use in a hydrogenation process in which a supporting catalyst is used is mixed with water or an aqueous composition containing an acid to form an extrudeable composition (also referred to as a target extruder). The target extruder is extruded to form a shape suitable for use in a hydrogenation process, such an extruded shape is also referred to herein as a “pil.” The pill is then dried, which typically includes calcination to form a dried target extruder.

[0078] In the first stage, the target dry extruder is impregnated with a solution containing a boron source (e.g., boric acid) and an inorganic compound selected from those described herein (e.g., citric acid). The resulting first-stage or intermediate impregnation composition is subjected to a first-stage calcination process at a temperature and time that significantly reduces its moisture content. After calcination, the intermediate may exhibit a measured loss on ignition (LOI) level of, for example, greater than 0% by weight and less than about 5% by weight, and the first-stage calcination process may be referred to herein as "complete combustion".

[0079] As a result, most, though not all, of the organic compounds are decomposed and therefore volatilize from the impregnated first-stage composition, and at the same time, most, though not all, of the water volatilizes (the degree of volatilization is measured and characterized by the LOI value), and the boron source is converted to B2O3.

[0080] In the second stage, the intermediate boron-containing inorganic oxide from the first stage undergoes a second impregnation using a metal-containing solution containing a target catalytically active metal and other optional or preferred components that are potentially beneficial to catalysis in the intended hydrogenation process, optionally containing phosphorus. After the second impregnation, the composition is subjected to a second calcination process, sometimes referred to herein as “partial combustion,” at a lower intensity temperature and / or time compared to the first, so that the resulting composition exhibits an LOI of preferably about 2 to about 15% by weight, or about 3 to about 7% by weight, for example, about 5% by weight.

[0081] Step-by-step overview of the preparation method 1. Based on the supporting catalyst required in the hydrogenation process, an inorganic oxide (optionally, a mixture of inorganic oxides, e.g., alumina + silica or silica-alumina) is selected for impregnation, which will hereafter be referred to as the "extruded material". The extruded material may be pre-prepared by mixing the selected inorganic oxide with water and optionally an acid such as nitric acid, extruding the mixture to form a pill of the desired shape, and firing the pill to form the extruded material. 2. Determine the type and concentration of metal present in the extruded material, its LOI (Liquid Indication) if present, and the volume of water pores. 3. Weigh the desired amount of extruded material from step 1. 4. Select the target weight percentage for B2O3. 5. Convert the target weight percentage to the mass of B2O3. Convert the mass of B2O3 to the mass of H3BO3 by multiplying by the conversion rate in 6.0.566 (if boric acid is the boron source used). 7. Based on the measurement of the nitrogen pore volume of the inorganic oxide, calculate the total amount of water required to fill the total pore volume of the dry inorganic oxide, and this amount also represents the maximum amount of water available for boron dissolution. 8. Calculate the amount of selected organic compound, such as citric acid, required to dissolve the selected boron source compound. Typically, a simple preliminary dissolution test at a selected temperature, e.g., 100°F (37.8°C), will establish the amount required to obtain an aqueous solution of a given combination of organic compounds and types and amounts of boron source. For example, using a combination of citric acid and boric acid, it was determined that the amount of citric acid required to dissolve boric acid at approximately 100°C is approximately 5.14 times the mass of boric acid. 9. Add the measured amounts of boron source (e.g., boric acid) and organic compound (e.g., citric acid) to a 200 mL beaker and dilute the contents with the calculated amount of water. 10. Add the watch glass and stirring rod to the beaker and begin stirring. 11. Gently heat the solution on a hot plate to a temperature of 110°F or less until the solution becomes clear. The first stage of standard pore volumetric impregnation (PVI) is performed by adding 12,200 g of the extruded material (on a dry basis) and the (boric acid / citric acid) solution from step 11 to a plastic measuring container, and then the container is sealed. 13. Rotate the container on a tumbler for about 1 hour, checking the contents periodically while rotating to ensure the mixture is moist, and adding a small amount of water if necessary (a dry appearance indicates that a small amount of water needs to be added to ensure the pores of the extruded material are filled). 14. Remove the container from the tumbler, remove the lid, and let it sit for about an hour. 15. Prepare the rotary firing furnace by cleaning the firing tubes and performing the first stage of "complete combustion" to determine suitable firing conditions for achieving the selected LOI, for example, an LOI of about 1% by weight. 16. As an example, a suitable firing program may start at 250°F, hold for 10 minutes, raise to 950°F over 40 minutes, and remain at 950°F for 40 minutes. In such a program, the firing tube must first be preheated to 250°F before the program is executed. 17. Add the impregnation material from step 14 to the firing tube, start a suitable airflow, e.g., 8SCFM, and run the firing program. 18. After the firing program is complete, allow the boron-containing intermediate to cool completely and measure the LOI to confirm that the target LOI level, for example, approximately 1% by weight as described above, has been achieved. 19. Select a target catalyst metal for the supporting catalyst and optionally phosphorus, and prepare a solution containing the metal (and phosphorus) for the second-stage PVI. 20. Conduct the second stage of PVI using the same format as described in steps 12-14. 21. To reach the target LOI, for example, about 5% by weight, select and set a second firing program as needed for "partial combustion". For example, a suitable second firing program to achieve an LOI of about 5% by weight may start at 320°F, hold for 10 minutes, raise to 670°F over 40 minutes, and remain at 670°F for 10 minutes. 22. Add the impregnation material from step 20 to the firing tube, start a suitable airflow, e.g., 8SCFM, and run the firing program. 23. After firing, the impregnated catalyst is quickly removed and its LOI is measured to confirm that the target LOI, for example, approximately 5% by weight, has been achieved.

[0082] Surprisingly, the pore size distribution (PSD) of the modified inorganic porous oxide, referred to as the "post-first PVI" intermediate, after the first-stage pore volume impregnation using a boron source and organic compounds, followed by "complete combustion," was found to contain a peak at 60 Å that was not present in the original inorganic oxide. Even more surprisingly, when the PSD was measured again after the "post-second PVI" product, or the supported hydrogenation catalyst of the present invention, following a second PVI and "partial combustion" to form the supported catalyst, the peak at 60 Å was no longer present. (See Figure 1).

[0083] Compositional effects of the method for preparing a support catalyst As will be demonstrated in the following examples, the two-step preparation method described herein yields a supported hydrogenation catalyst with unexpectedly superior catalytic performance. Furthermore, careful analysis of the supported catalyst revealed an unexpected effect on the distribution of at least some of the catalytic metals and phosphorus in the supported catalyst particles or pills. Rather than the metals and phosphorus being uniformly distributed throughout the particles, the distribution is heterogeneous, with high concentrations of group VIB metals or multiple metals and phosphorus on and near the outer surface of the particles, and low concentrations in the center of the particles.

[0084] An example of the heterogeneity of elemental composition distribution in a supported catalyst pill prepared according to the present invention is shown graphically in Figure 2, which shows the typical metal concentrations in the cross-section of the extruded pill or particle using electron probe microanalysis (EPMA) according to the test procedure described below. In EPMA, a target sample, in this case an extruded piece cut in half horizontally, is struck with a focused electron beam that emits X-rays correlated with a specific selected element, moving across the sample (from position 0 to position 1 in Figure 2). In EPMA plots, such as the typical plot in Figure 2, the x-axis represents the position across the pill, and the y-axis represents the relative intensity, and therefore the concentration of the specific element. Also shown in Figure 2 is an electron micrograph of a cross-section of an asymmetrical tetrahedron-shaped supported catalyst extruded particle or pill, identifying the longitudinal position in the length direction from one leaf edge (0) to the other leaf edge (1). In this figure, the particle has a tetrahedron shape, but the same effect is expected for other extruded particle or pill shapes. As shown in a typical EPMA plot, this method enables the determination of cases where a significantly heterogeneous metal concentration distribution exists from one outer edge of the particle to the opposite outer edge of the pill along the central line passing through the pill.

[0085] EPMA is capable of mapping the spatial distribution of major and minor elements within a solid sample, and is applied herein in this manner to supporting catalyst pills or particles. Generally, the sample is tested by embedding it in a resin or polymer matrix and polishing it to obtain a flat surface. Calibration is performed against mineral standards. This test provides a combination of elemental mapping and high-resolution imaging in an electron microscope.

[0086] The observed and measured concentrations have also been converted to numerical values, as reported in the tables related to the examples described below. Unexpected concentration distributions were observed for group VIB metal oxides, including molybdenum oxide and tungsten oxide, as well as phosphorus oxide (P2O5). In contrast, group VIIIB metal oxides used in combination with group VIB metal oxides and phosphorus oxide (if present) were not distributed as heterogeneously, as is also shown in the figures and the data reported in the examples. When the method according to the present invention is carried out, the following ranges of values ​​are expected for the distribution of group VIB metal oxides and phosphorus oxide along the centerline passing through the cross-section of the supporting catalyst particles.

[0087] [Table 2]

[0088] Improvement of catalytic activity As described above, by carrying out the method of the present invention, a supported catalyst exhibiting improved catalytic activity is produced when the catalyst is used in a hydrogenation process. For the following reasons, catalytic activity is commonly expressed in degrees F (°F) in the art: When a supported catalyst is used in a hydrogenation process for the removal of sulfur or nitrogen, the level of sulfur or nitrogen in the treated hydrocarbon product is measured in correlation with the operating temperature of the process. Operating at a higher temperature results in a lower content of sulfur or nitrogen in the treated product, but doing so incurs higher costs for operating at the higher temperature. Plotting the achieved sulfur or nitrogen content against the operating temperature yields a graph referred to as an ST or NT plot, where the performance is interpolated to a specific sulfur or nitrogen target. Given the practical difficulties that would be encountered in evaluating catalyst performance in a full-scale industrial installation, catalyst performance is typically evaluated at three different temperatures in a pilot plant to produce a linear regression of performance in an ST or NT plot. For example, when evaluating catalyst performance in a process for producing ultra-low sulfur diesel (ULSD) applications corresponding to the evaluation process reported in the examples, a typical target would be to achieve a concentration of 10 ppmS or 10 ppmN in the product using a supporting catalyst.

[0089] Referring to Figure 3, to obtain a treated diesel product containing a reduced sulfur content of 10 ppm S using a typical prior art ("comparative") Mo / Co-containing catalyst B (corresponding to supported catalyst E in Table 7 below), it is necessary to operate the pilot plant at a temperature of 660°F (348.9°C). In contrast, using the supported Mo / Co-containing catalyst prepared according to the method of the present invention disclosed herein, it is necessary to operate the pilot plant at only about 646°F (341.1°C) to achieve the same reduced level of S of 10 ppm. Thus, the improved catalytic activity of the supported catalyst of the present invention can be expressed as being more active than the prior art catalyst in a typical hydrodesulfurization process by a difference of 660°F - 646°F = 14°F. The catalytic performance reported in the examples herein is also expressed in units of °F.

[0090] While alternative methods exist to express improvement, such as the percentage of S or N removal, in processes that produce ULSD, the degree of removal is always far above 90%, and therefore, relative changes in the removal percentage may be subject to significant fluctuations due to the low levels of residual S or N. Alternatively, relative changes in the HDS or hydrodenitrification (HDN) rate constant, or relative volume activity can be used. However, it is preferable to express the improvement in degrees F so that the improvement can be reported as X°F better than the reference supporting catalyst.

[0091] Furthermore, to those skilled in the art, a 5°F improvement typically distinguishes a new or improved supported catalyst from an existing catalyst, and achieving such an improvement would be expected to require considerable research effort, perhaps several years of work. Achieving an even greater improvement of 10°F would be considered an even more remarkable leap forward by those skilled in the art, but doing so could require several years of research and development. Anything above 10°F is considered a significant improvement. Thus, as will be observed in the examples reported herein, the supported catalysts produced according to the method of the present invention exhibit an improvement of at least 14°F in performance, which was surprising and unexpected. In summary, it has been observed that the method of the present invention can produce a supported catalyst exhibiting improved catalytic performance as defined above, from 5°F to a maximum of 26°F, or from 6°F, or 7°F, 8°F, 9°F, 10°F, 11°F, 12°F, 13°F to 26°F, or 25°F, or 24°F, or 23°F, or 22°F, or 21°F, or 20°F, or 19°F, 18°F, or 17°F, or 16°F, or 15°F, or 14°F, or 13°F, or 12°F, or 11°F, each of which is represented by the intervening values ​​and combinations of the values ​​described above.

[0092] Test method Loss on ignition (LOI) LOI is a measure of total volatile matter present in a sample, such as porous inorganic oxides, catalyst compositions supported on inorganic oxides, or such oxides impregnated with various additives, including precursors or intermediates of such catalysts. Volatile matter is considered to consist of, or essentially consists of, water and thermally and / or oxidatively decomposable organic components or residues. For the purposes of this disclosure, the LOI test is performed by exposing the sample to an oxygen-containing atmosphere at 1020°F (548.9°C) for 1 hour, thereby oxidizing, decomposing, or igniting organic matter and displacing all, but most, of such matter and residual water in the catalyst.

[0093] Electron probe trace analysis (EPMA) EPMA is approximately 100 mg / kg -1 This test method (further described below) combines the imaging capabilities of a focused electron beam with the analytical capabilities obtained by induced X-rays to produce spatial resolution analysis of a wide range of elements with a detection limit. EPMA is capable of mapping the spatial distribution of major and minor elements within a solid sample, and is applied herein in this manner to supporting catalyst pills or particles. Generally, the sample to be tested is embedded in a resin or polymer matrix and polished to obtain a flat surface. Calibration is performed against mineral standards. This test provides a combination of elemental mapping and high-resolution imaging in an electron microscope.

[0094] Sample preparation: For imaging and scanning of the sample cross-section, the sample was placed in epoxy resin and allowed to cure overnight at room temperature. The sample stub was then cut with a diamond blade and polished to a smooth surface using 6-micron and 0.25-micron diamond paste. A thin carbon coating was applied to the sample stub for better conductivity.

[0095] EPMA Test Procedure: A JEOL JXA-8230 electron probe microanalyzer (EPMA) equipped with four wavelength dispersive spectrometers (WDS) was used to perform a linear scan of the sample cross-section (from the end of one leaf to the end of the opposite leaf) at 25 kV and 20 nA. PET crystals were used for the detection of P and Mo, TAP for W, and LiF for Ni. The residence time was 500 milliseconds, and the step size was approximately 1 micron.

[0096] Examples In the following examples, porous inorganic oxide support particles were prepared from a mixture of alumina, 2-4 wt% silica, water, and a small amount of nitric acid. This mixture was extruded and calcined (to a moisture level of about 5 wt%) for subsequent processing according to the methods disclosed herein to prepare porous particles or pills, also referred to herein as “extruded products,” in the asymmetrical four-leaf clover shape shown in Figure 2. The extruded products exhibited the following properties: surface area (SA) = 200-300 m² 2 / g, and pore volume = 0.7~1.0 cc / g. Compositions produced in commercial, semi-commercial, or pilot plant environments typically contain recirculated catalyst powder together with alumina and / or alumina + silica mixtures. Therefore, it is expected that small amounts of Group VIB, Group VIIIB, and / or phosphorus may be present in the preliminary or intermediate catalyst composition. However, measuring the metal or metal oxide in such intermediate compositions allows for adjustment of the additional amounts of metal and phosphorus compounds to achieve the desired final or target concentrations in the final catalyst. Conversely, the presence of small amounts of metal oxides other than those targeted in the final catalyst (e.g., less than 1 wt% nickel oxide in a molybdenum oxide + cobalt oxide catalyst) has not been shown to be detrimental to the final performance of the catalyst or to significantly affect its performance.

[0097] Example 1 The components used to prepare the support in the first stage described above were the extruded material described immediately prior to, H3BO3 (boric acid) as the boron source, citric acid as the organic compound in the first stage, and Co and Mo as catalytic metals in the impregnation in the second stage. 200 g of the extruded material was weighed (on a dry basis, i.e., with moisture content adjusted), and a target weight percentage of B2O3 was selected as 3.0 wt%, and the corresponding mass of B2O3 required was calculated to be 6.19 g. The mass of B2O3 was converted to the mass of H3BO3 by multiplying it by a conversion factor of 0.566, thereby obtaining that the required amount of H3BO3 was 10.9 g. The maximum volume and amount of water available for boron dissolution was established by the total pore volume of the extruded material based on the nitrogen pore volume described above. The pore volume was determined to be 0.8 cc / g, and multiplying this by 200 g of dry extruded material, the required amount of water was obtained to be 160 cc. The amount of citric acid needed to dissolve the calculated amount of boric acid was separately determined to be 5.14 times the mass of boric acid, which corresponded to 56.03 g of citric acid. In subsequent examples where a different organic acid (e.g., acetic acid, malic acid, etc.) was used instead of citric acid, the same molar ratio of carboxylic acid to boric acid was used.

[0098] The above amounts of boric acid and citric acid were added to a 200 mL beaker and diluted with the calculated amount of water. A watch glass and stirring rod were added to the beaker, and the contents were stirred while gently heating the contents to a temperature of 110°F (43.3°C) or less until a clear solution was obtained.

[0099] The first stage of pore volumetric impregnation (PVI) was performed by adding 200 g of extruded material (dry basis) and boron / citric acid solution to a plastic measuring container and rotating it on a tumbler for 1 hour. During this time, the contents were periodically checked to ensure that the mixture was moist, and small amounts of water were added as needed to ensure that the pores of the extruded material were filled. The container was removed from the tumbler, the lid was removed from the container, and it was left to stand for 1 hour.

[0100] The rotary firing furnace was prepared by cleaning the firing tube and preheating it to 250°F (121.1°C). The firing program was set to achieve an LOI of approximately 1 wt% of the firing composition as follows: holding at an initial temperature of 250°F (121.1°C) for 10 minutes, followed by raising to 950°F (510°C) over 40 minutes, and finally a 40-minute residence or holding period at 950°F (510°C). The impregnated material was added to the firing tube, the airflow was started at 8 SCFM, and the firing program was executed. After the completion of the program, the first stage firing composition was cooled to near ambient temperature, and its LOI was measured to confirm that it was approximately 1 wt%.

[0101] A metal solution containing Co and Mo (or Ni and Mo in Example 3 below) for the second stage of PVI was prepared, and PVI impregnation was carried out in the same manner as described above for the first stage of impregnation. The target weight % of the solution is summarized in the table below.

[0102] [Table 3]

[0103] The second stage firing program was set to achieve an LOI of approximately 5 wt% of the firing composition, as follows: an initial temperature of 320°F held for 10 minutes, followed by a rise to 670°F over 40 minutes, and finally a 10-minute dwell or holding period at 670°F. The second stage impregnation material was added to the firing tube, the airflow was started at 8 SCFM, and the firing program was executed. After firing, the catalyst was rapidly removed, and the LOI was measured to confirm that limited or partial combustion achieved the target LOI of approximately 5 wt%.

[0104] Reference support samples or control support (CS) samples corresponding to Example 1 were also prepared, but the first stage of impregnation using boron and citric acid and the first stage of calcination were not performed. Therefore, no boron-containing composition was produced.

[0105] The resulting chemical composition of the support catalyst is shown in Table 4 and in Example 3 below. The pore size distribution of the extruded material, the first-stage boron-impregnated inorganic oxide, and the final support catalyst is shown in Figure 1.

[0106] Example 2 Example 1 was repeated to demonstrate the reproducibility of the method for preparing the catalyst and the performance activity of the resulting catalyst. The chemical composition of the resulting supporting catalyst is shown in Table 4 and Example 3 below.

[0107] Example 3 The catalyst in Example 3 was prepared using the same method as in Examples 1 and 2, but the target catalyst metals were Ni and Mo. The control sample was also prepared using the same method, but without the addition of boron, and therefore PVI was not required in the first step. The resulting chemical compositions of the supporting catalysts in Examples 1 to 3 are shown in the table below.

[0108] [Table 4]

[0109] Table 5 below summarizes the comparison of catalyst compositions and properties for Examples 1 and 2 (Co / Mo catalysts) and the control and Example 3 (NiMo catalyst). The Co / Mo and Ni / Mo examples of the present invention were designed to be compositionally similar to the corresponding control formulations. Essentially, the only difference between the examples of the present invention and the control examples is the incorporation of the two-step PVI of B described herein in the examples of the present invention.

[0110] [Table 5]

[0111] In the performance testing laboratory, the catalytic activity of the above samples was evaluated using laboratory-blended diesel feed according to the ultra-low sulfur diesel (ULSD) test protocol. The temperature and pressure conditions of the two-week test protocol are shown in Figure 4. In the figure, "TOS(h)" means "time on stream" or the time the test unit is running. Three different temperature conditions were used, as will be observed, and these conditions are as follows and are referred to in the figure: different temperature and pressure conditions were used for the C0M0-containing catalyst versus the NiMo catalyst. The characteristics of the blended diesel feeds of C0M0 and NiMo formulations are shown in Table 6 below.

[0112] [Table 6]

[0113] For performance testing and property comparison, the catalysts of the present invention in Examples 1 and 2 were compared to the CS control or reference catalyst ("baseline") identified as baseline (Mo / Co) in Table 5 above, and the catalyst of the present invention in Example 3 was compared to the CS control or reference catalyst identified as baseline (Mo / Ni) in Table 5 above. For both the Co / Mo and Ni / Mo compositions, the hydrodesulfurization (HDS) activity and hydrodesulfurization (HDN) activity were calculated by determining the S and N content in the liquid product of the units at 1-day intervals, respectively. Dynamic regression was performed to determine the activity compared to the control or reference catalyst. The difference in HDS activity was expressed in units of Fahrenheit (°F) and normalized by 10 ppmS. The difference in HDN activity was expressed in units of improvement percentage compared to the control or reference (baseline) catalyst at each temperature condition.

[0114] The activity data presented in Figures 5 and 6 clearly demonstrate the advantages of the method of the present invention, which includes a two-step impregnation for B incorporation. B incorporation via the method of this disclosure produced higher activity supporting catalysts for both Co / Mo-containing and Ni / Mo-containing distillate hydrogenation (DHT) compositions when tested under several different conditions. These tests were conducted on the catalyst composition of the present invention, identified as Method of the Present Invention (Mo / Co) in Table 5 above, and its iterations, Method of the Present Invention (Mo / Co). * Compared to its reference or control catalyst (a catalyst containing Mo and Co) identified as baseline (Mo / Co) in Table 5 above, the catalyst exhibited an improvement of approximately 12°F in HDS activity and an improvement of approximately 50% in HDN activity. The catalyst of the present invention, identified as method (Mo / Ni) in Table 5 above, exhibited approximately 15°F better HDS activity and approximately 30% better HDN activity compared to its control or reference catalyst (a catalyst containing Mo and Ni) identified as baseline (Mo / Ni) in Table 5 above. See Figure 6.

[0115] Comparative Example Comparison with alternative techniques To compare alternative methods for incorporating boron into hydrogenation catalysts, the following CoMo-containing catalysts were prepared and compared with the methods of the present invention as shown in the above examples disclosed herein. In each case, the control support base CS refers to the support identified and characterized in Table 5 above. In addition, support containing a mixture of alumina and silica was also used for comparison. The following methods were compared.

[0116] A. CS / B+CA PVI on a support, first firing stage, metal PVI, second firing stage. The method of the present invention as disclosed herein.

[0117] B. CS / metal solution → B-CA First, a metal solution was impregnated into a support, and the resulting intermediate composition was calcined using the "complete combustion" method described above. Subsequently, the resulting metal-impregnated support was further impregnated with a solution containing boron and citric acid, and the resulting impregnated composition was calcined using the "partial combustion" method disclosed herein. The resulting support catalyst was tested to determine the effect of the boron impregnation sequence on the catalytic performance. C. CS / metal solution+B A Co / Mo metal solution containing citric acid and as much boric acid as possible that could be dissolved before causing destabilization of the solution was impregnated into the CS base. This produced a supporting catalyst containing approximately 0.7 wt% B2O3, the maximum possible amount achievable through this impregnation approach.

[0118] D. Alumina + Silica - Alumina + B / Metal Solution In this method, for example, boric acid was added to alumina and silica-alumina additive (25% by weight) using an indirect heat exchanger that utilizes cap screws for heating, cooling, or drying the bulk solid (a commercially available version of this technology is Holo-Flite® Thermal Processor). The extruded material was then impregnated with the same metal solution as the composition of the present invention, and the resulting impregnated catalyst was calcined via partial combustion.

[0119] This method was used to compare the effect of adding boron during the mixing or kneading process with the effect of impregnating with boron as a component of the impregnation solution.

[0120] E. Metal solution / CS The support material was impregnated with a metal solution, followed by firing, without the addition of boron or citric acid.

[0121] Table 7 and Figure 7 (pore size distribution) below summarize the characteristic data of the supported catalyst prepared according to the alternative method described above and Example 1 according to the method of the present invention as described herein.

[0122] [Table 7]

[0123] The activity data is presented in Figure 8, clearly demonstrating the advantages of the two-step impregnation method of the present invention for boron incorporation. As can be observed, boron incorporation using an indirect heat exchanger, incorporating boron together with an inorganic oxide before metal solution impregnation (Al2O3 / silica-alumina + boron, followed by metal solution impregnation and then calcination, identified as D above), resulted in a catalyst exhibiting approximately 6°F better HDS activity compared to the baseline method of impregnating the support with a metal solution in the absence of boron(E) and then calcining. In contrast, the supported catalyst prepared according to the method of the present invention (CS / B + CA PVI on a support, first-step calcination, metal PVI, second-step calcination, identified as A above) and corresponding to Example 1, exhibited approximately 12°F better HDS activity than the same baseline method. These results demonstrate that while boron enhances HDS activity, specific means of achieving boron incorporation are crucial to maximizing the activity enhancement achieved by boron incorporation. In other words, boron incorporation via impregnation results in improved activity compared to direct incorporation of B in combination with an alumina support.

[0124] Regarding the introduction of boron through impregnation, referred to as pore volume impregnation (PVI), these results clearly demonstrate that the order of addition significantly affects the activity. Again, the supported catalyst prepared according to the method of the present invention illustrated in Example 1 (CS / B + CA PVI on the support, first-step calcination, metal PVI, second-step calcination) exhibited HDS activity approximately 12°F better than the baseline supported catalyst E. Reversing the order of the impregnation steps, as in "B" (metal PVI on the support, calcination, followed by boron and CA PVI, then calcination), resulted in a catalyst with no promoting effect compared to the baseline catalyst (in fact, referring to Figure 8, a slight loss of activity compared to the baseline is observed). Boron introduced via co-impregnation into "C" (metal, boron, CA PVI on the support, then calcination) exhibited a significant loss of activity of approximately 7°F.

[0125] The activity results for HDN followed a similar trend, with conditions 1-3 and “Overall” identified in the figure referring to the same conditions identified above and shown in the attached figure. Overall, method C yielded no promoting effect compared to the baseline supported catalyst, the supported catalyst by method B showed an overall improvement of about 36%, and the catalyst by method D showed an overall improvement of about 27%. In contrast, the highest promoting effect was observed using the supported catalyst prepared in Example 1, in other words, the supported catalyst prepared according to the method of the present invention disclosed herein (referred to above as A, summarized as CS / B+CA PVI on a support, first-step calcination, metal PVI, second-step calcination), which showed an overall improvement of about 65%.

[0126] Further comparative methods were evaluated and compared with the methods of the present invention disclosed herein. To further demonstrate the advantages of boron / carboxylic acid (specifically citric acid)-containing solutions, alternative Co and Mo-containing support catalysts were prepared using different impregnation chemicals.

[0127] F. CS / B-NH3→Metal solution PVI A control inorganic oxide base (CS) was impregnated with a solution containing boric acid dissolved in a basic ammonia solution. The resulting boron-containing intermediate was calcined using the “complete combustion” method described herein above. The resulting particles were impregnated with the same metal solution as described in the above examples, and the resulting impregnated catalyst composition was calcined using the partial combustion method described herein above. The composition and method are consistent with an alternative two-step PVI method that uses ammonia to incorporate boron.

[0128] G. CS / B-CA → Modified metal solution (Zero-P) In this example, the supporting catalyst was prepared as in Examples 1 and 2 of the present invention above, with the notable exception that the Co and Mo-containing metal solution did not contain phosphoric acid. This example was selected to evaluate the effect of the absence of P on the activity of the resulting supporting catalyst.

[0129] Table 8 summarizes the characterization data for catalysts F and G, and Figure 9 shows their pore size distributions.

[0130] [Table 8]

[0131] The performance of catalysts F and G was also evaluated in comparison to the “baseline” reference support catalyst E, as in the above examples, and the performance results are shown in Figure 10. As can be observed, the two-step PVI method for boron incorporation described herein is improved over the alternative method described in F. Examples 1 and 2 perform better than equivalent boron incorporation methods that use ammonia to promote boron dissolution by about 10°F for HDS. Furthermore, the formulations in Examples 1 and 2 containing P were about 5°F better for HDS compared to equivalent methods that do not contain phosphorus. A similar trend was observed for HDN activity.

[0132] Alternative organic compounds Further research was conducted on the usefulness of alternative organic compounds, such as chelators or chelating agents and modifiers, to be used in conjunction with the boron source to prepare the first-stage boron-impregnated solution. As disclosed in the above examples, citric acid is particularly preferred, but other organic compounds disclosed herein are also useful, and NH4OH was also evaluated. The following examples illustrate the results of such research.

[0133] Boron-containing intermediates were prepared to demonstrate that a wide variety of hydroxycarboxylic acids can be used to promote the dispersion or dissolution of boron in aqueous compositions for the first stage of impregnation. Table 9 and related Figures 11 and 12 below demonstrate that various mono- and di-carboxylic acids, including citric acid, acetic acid, oxalic acid, maleic acid, malic acid, and malonic acid, can be used to prepare useful boron-impregnating compositions according to the method of the present invention. In addition, NH4OH, phosphoric acid, and water itself were tested. Similar peaks were observed in the pore size distribution curves after the first stage of impregnation and calcination for most of these carboxylic acids, at approximately 25 Å to 50 Å; see Figure 11.

[0134] [Table 9]

[0135] The HDS activity of supported catalysts prepared according to the present invention as disclosed herein, and alternatively using citric acid, malic acid, maleic acid, and oxalic acid (summarized in the table above), was compared with the baseline supported catalyst shown in Figure 12, and pilot plant tests were conducted as described above. The baseline supported catalyst was the same as reported above, i.e., a silica-alumina inorganic oxide support impregnated with a solution of the same catalytically active metal (except for the absence of boron) as the catalyst of the present invention. As shown in Figure 12, the catalysts of the present invention performed better than the baseline supported catalyst, with citric acid showing the best performance.

[0136] Compositionally different characteristics The novel method for producing boron-containing supported catalysts described herein also yields remarkable compositional differences in supported catalysts produced according to the disclosed method compared to supported catalysts produced by other methods.

[0137] Particles or pills (extrudeds) of boron-supported catalyst produced according to the present invention were analyzed using an electron probe microanalyzer (EPMA). The test method is described above, an exemplary test diagram is shown in Figure 2, and the test results are discussed in Table 2. EPMA testing of catalyst pills demonstrated that boron addition by the method disclosed herein affects how the catalyst metal and phosphorus are distributed throughout the extruded material. Prior to the invention disclosed herein, it was generally considered preferable for the metal or active catalyst component to be uniformly distributed throughout the supported catalyst pill. However, surprisingly, EPMA testing confirmed that preparing the catalyst according to the method of the present invention to produce a non-uniform distribution throughout the particles or pill resulted in improved performance of the supported catalyst, see, for example, Figure 10 and the performance data summarized in the related table.

[0138] The distribution of metals and phosphorus is not uniform throughout the entire pill; rather, it is heterogeneous, with higher concentrations of group VIB metals or multiple metals and phosphorus in the outer edges and vicinity of the pill, and lower concentrations in the central region of the pill.

[0139] Examples A–E described above were evaluated using EPMA. The results for phosphorus, cobalt, and molybdenum, respectively, are summarized in Table 10 below and shown in Figures 13–15. Figure 16 shows scans of selected samples A, D, and E (also listed in Tables 7 and 10), which are extracted from Figures 13–15 and therefore easier to read, but lead to the same conclusions.

[0140] [Table 10]

[0141] As shown in Table 10 and the figures, unexpectedly, the supported catalysts prepared according to the method of the present invention disclosed herein show higher concentrations of Mo and P near the edges or outer third of the particle leaves compared to supported catalysts prepared according to alternative or comparative methods. However, the same heterogeneity is not observed for CO. On the other hand, the unexpected and distinct concentration profiles are consistent with the demonstrated and improved catalytic performance observed in the supported catalysts prepared according to the method of the present invention disclosed herein.

[0142] Additional supporting catalyst samples containing tungsten, nickel, and other catalyst components were prepared according to the methods disclosed herein and tested using EPMA. Catalyst characteristics, composition, and EPMA properties are summarized in Tables 11-13 below, compared to control or comparative samples. The results were similar to those reported above, namely the positional compositional distributions specific to group VIB metals including Mo and W, and P; however, group VIIIB metals Co and Ni did not exhibit the same response.

[0143] [Table 11]

[0144] [Table 12]

[0145] [Table 13]

[0146] The following paragraphs describe various alternative embodiments of the present invention. 1. A method for producing a supporting catalyst, wherein the method is (a) Porous inorganic oxide catalyst carrier or carrier extruder, (i) Boron-containing source, (ii) an aqueous solution, dispersion, or suspension containing an organic compound or organic chelating agent selected from organic compounds containing at least two oxygen atoms and 2 to 10 carbon atoms, Forming a carrier composition containing boron and an organic compound, and optionally extruding the composition to form an extruded product. (b) The composition or extruded in (a) is calcined, or dried and calcined to reduce its volatile content to a level of more than 0% by weight and about 5% by weight as measured by loss on ignition (LOI), (c)(b) is impregnated with a solution, dispersion, or suspension containing at least one group VIB metal-containing component or source and at least one group VIIIB metal-containing component or source. (d) Including firing or drying and firing the composition formed in accordance with the impregnation step (c) to reduce its volatile content to a level of more than 0% by weight and less than about 30% by weight as measured by loss on ignition (LOI), (1) The amount of the boron-containing source is expressed as boron oxide B2O3 and is sufficient to form a supporting catalyst having a boron content in the range of about 1% to about 13% by weight, based on the total weight of the catalyst. (2) A method in which loss on ignition (LOI) is measured by subjecting the weighed sample to an oxygen-containing atmosphere at 1020°F (548.9°C) for 1 hour and measuring the weight loss of the sample. 2. The method according to Embodiment 1, wherein the boron content of the generated supporting catalyst is expressed as boron oxide B2O3 and is in the range of about 1.5% by weight to about 6% by weight based on the total weight of the catalyst. 3. The method according to Embodiment 1 or Embodiment 2, wherein the boron content of the generated supporting catalyst is expressed as boron oxide B2O3 and is in the range of about 2% to about 5% by weight based on the total weight of the catalyst. 4. The method according to any one of Embodiments 1 to 3, wherein the solution, dispersion, or suspension in step (c) further comprises a phosphorus source, expressed as oxide P2O5 and based on the total weight of the catalyst, to provide a phosphorus content of about 0.5% to about 10% by weight of the supporting catalyst. 5. The method according to Embodiment 4, wherein the amount of the phosphorus source is expressed as oxide P2O5, and based on the total weight of the catalyst, results in a phosphorus content of the supporting catalyst in the range of about 0.5% to about 5% by weight or about 4% to about 10% by weight. 6. The method according to any one of Embodiments 1 to 5, wherein the boron-containing source is selected from meta-boric acid (HBO2), orthoboric acid (H3BO3), ammonium borate tetrahydrate [(NH4)2B4O7.4H2O], sodium tetraborate, ammonium borate, ammonium tetraborate [(NH4)2B4O7], boron oxide (B2O3), lithium tetraborate, mono-, di-, or trialkylborate amines, ammonium tetraphenylborate, organoboron compounds, and mixtures thereof. 7. The method according to any one of Embodiments 1 to 6, wherein the organic compound or chelate is selected from organic compounds comprising at least two oxygen atoms and 2 to 10 carbon atoms, and ethers, esters, acetals, acid chlorides, acid amides, oligomers, or polymers thereof, and / or (ii) organic compounds comprising at least one covalently bonded nitrogen atom and at least one carbonyl moiety. 8. The method according to any one of Embodiments 1 to 7, wherein the organic compound is selected from acetic acid, citric acid, tartaric acid, oxalic acid, maleic acid, malonic acid, malic acid, butanediol, pyruvaldehyde, glycolaldehyde, acetaldol, tartaric acid, ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, tetrapentylene glycol, polyethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether, and mixtures thereof. 9. The method according to any one of Embodiments 1 to 8, wherein the boron source contains boric acid and the organic compound contains citric acid. 10. The method according to any one of Embodiments 1 to 9, wherein the solution, dispersion, or suspension in step (c) comprises at least one organic chelating agent selected from (i) organic compounds comprising at least two oxygen atoms and 2 to 10 carbon atoms, and ethers, esters, acetals, acid chlorides, acid amides, oligomers, or polymers thereof, and / or (ii) organic compounds comprising at least one covalently bonded nitrogen atom and at least one carbonyl moiety. 11. The method according to Embodiment 10, comprising an organic chelating agent selected from acetic acid, citric acid, oxalic acid, maleic acid, malonic acid, malic acid, ethylene glycol, and ammonium bicarbonate. 12. The method according to any one of embodiments 1 to 11, wherein the ignition loss after step (b) is greater than 0 to about 2% by weight. 13. The method according to any one of Embodiments 1 to 12, wherein the catalyst exhibits a ignition loss of about 3 to about 7% by weight after step (d). 14. The method according to any one of Embodiments 1 to 13, wherein the porous inorganic oxide is selected from eta, theta, or gamma alumina and mixtures thereof, silica, silica-alumina, alumina in which silica-alumina is dispersed, silica-coated alumina, alumina-coated silica, magnesia, zirconia, titania, titania-alumina, and mixtures thereof. 15. A support catalyst formed according to any one of Embodiments 1 to 14. 16. A method comprising hydrogenating a hydrocarbon feed by contacting the hydrocarbon feed with the support catalyst described in Embodiment 15 under hydrogenation conditions. 17. A method for producing an inorganic oxide catalyst support, wherein the method is (a) porous inorganic oxide in the form of fine particles, (1) Boron-containing source and (2) Combining with a composition comprising an aqueous solution, dispersion, or suspension containing an organic compound selected from the group consisting of compounds containing at least two oxygen atoms and 2 to 10 carbon atoms, (b) Extruding the combination in (a) to form an extruded product, (c) Including firing the extruded material to a dry level of more than 0% by weight to about 5% by weight as measured by the loss on ignition (LOT), (i) The boron-containing source is represented as boron oxide B2O3 and is present in an amount that provides a boron content in the range of about 1% to about 13% by weight, based on the total weight of the support. (ii) A method in which the loss on ignition is measured by subjecting the weighed sample to an oxygen-containing atmosphere at 1020°F (548.9°C) for 1 hour and measuring the weight loss. 18. The method according to Embodiment 17, wherein the boron content of the support is expressed as an oxide B2O3 and is in the range of about 1.5% by weight to about 6% by weight based on the total weight of the support. 19. The method according to Embodiment 18, wherein the boron content of the catalyst support is expressed as oxide B2O3 and is in the range of about 2% to about 5% by weight based on the total weight of the support. 20. In step (a), (1) The boron-containing source is selected from meta-boric acid (HBO2), orthoboric acid (H3BO3), ammonium borate tetrahydrate [(NH4)2B4O7.4H2O], sodium tetraborate, ammonium borate, ammonium tetraborate [(NH4)2B4O7], boron oxide (B2O3), lithium tetraborate, mono-, di-, or tri-alkylborate amines, ammonium tetraphenylborate, organoboron compounds, and mixtures thereof, wherein the organic compound contains citric acid. (2) The method according to any one of embodiments 17 to 19, wherein the organic compound or chelate is selected from organic compounds comprising at least two oxygen atoms and 2 to 10 carbon atoms, and ethers, esters, acetals, acid chlorides, acid amides, oligomers, or polymers thereof, and / or (ii) organic compounds comprising at least one covalently bonded nitrogen atom and at least one carbonyl moiety. 21. The method according to any one of Embodiments 17 to 20, wherein in step (a), the boron-containing source contains boric acid, and the organic compound or chelate contains citric acid. 22. The method according to any one of Embodiments 17 to 21, wherein the porous inorganic oxide is selected from eta, theta, or gamma alumina and mixtures thereof, silica, silica-alumina, alumina in which silica-alumina is dispersed, silica-coated alumina, alumina-coated silica, magnesia, zirconia, titania, titania-alumina, and mixtures thereof. 23. A supported hydrogenation treatment catalyst, A porous inorganic oxide catalyst support or catalyst support, At least one VIB group metal component in oxide form, At least one group VIIIB metal component in oxide form, Boron-containing components in the form of oxides represented as B2O3, Optionally, it includes a phosphorus component in the form of an oxide represented as P2O5, (a) The boron oxide content is in the range of 1 to 13% by weight, based on the total weight of the catalyst. (b) If present, the phosphorus content is approximately 0.5% by weight, based on the total weight of the catalyst. (1) Group VIB and VIIIB metal components, as well as phosphorus and boron components, are supported on and / or in a support or carrier containing alumina or silica in the form of a pill having an internal cross-section and an external surface. (2) The position traversing the internal cross-section of the pill is identified by the percentage of the distance along the centerline from the first edge of the pill cross-section, referred to as the starting point or 0%, to the furthest edge of the pill cross-section, referred to as 100%, (I) The concentration of group VIB metal oxides in the first 33 1 / 3% or the last 33 1 / 3% of the pill cross-section is approximately 20% to 100% higher than the concentration of group VIB metal oxides in the middle 33 1 / 3% of the pill cross-section. (II) A supported hydrogenation catalyst in which the concentrations of group VIB and group VIIIB metal oxide components, and, if present, phosphorus oxide components, are determined by electron probe trace analysis, extending to the outer surface across the cross-section of the pill. 24. The catalyst according to Embodiment 23, wherein the VIB group metal component is selected from molybdenum, tungsten, or chromium oxides. twenty five. The catalyst according to any one of embodiments 23 to 24, wherein the group VIIIB metal component is selected from cobalt or nickel oxides. 26. The catalyst according to any one of Embodiments 23 to 25, wherein the VIB group metal component comprises molybdenum or tungsten. 27. A catalyst according to any one of embodiments 23 to 26, comprising phosphorus. 28. The catalyst according to Embodiment 27, wherein the concentration of phosphorus oxide in the first 33 1 / 3% or the last 33 1 / 3% of the pill cross-section is about 30% to about 350% higher than the concentration of phosphorus oxide in the middle 33 1 / 3% of the pill cross-section. 29. The catalyst according to Embodiment 27 or 28, wherein the amount of phosphorus component is expressed as an oxide P2O5 and is in the range of 4% to 10% by weight based on the total weight of the catalyst. 30. The catalyst according to Embodiment 29, wherein the amount of phosphorus component is in the range of 4% to 7% by weight. 31. The catalyst according to Embodiment 30, which is expressed as an oxide B2O3 and has a boron content in the range of 2% to 8% by weight based on the total weight of the catalyst. 32. A catalyst according to Embodiment 31, with a boron content in the range of 4% to 6% by weight. 33. The catalyst according to any one of embodiments 23 to 32, wherein the carrier comprises alumina. 34. The catalyst according to any one of Embodiments 23 to 33, wherein the boron source contains boric acid. 35. The catalyst according to any one of embodiments 23 to 34, further comprising an organic additive. 36. The catalyst according to Embodiment 35, wherein the organic additive is selected from (i) organic compounds comprising at least two oxygen atoms and 2 to 10 carbon atoms, and ethers, esters, acetals, acid chlorides, acid amides, oligomers, or polymers thereof, and / or (ii) organic compounds comprising at least one covalently bonded nitrogen atom and at least one carbonyl moiety. 37. The catalyst according to any one of Embodiments 1 to 36, wherein the porous inorganic oxide is selected from eta, theta, or gamma alumina and mixtures thereof, silica, silica-alumina, alumina in which silica-alumina is dispersed, silica-coated alumina, alumina-coated silica, magnesia, zirconia, titania, titania-alumina, and mixtures thereof.

[0147] In this specification, the present invention has been described with reference to specific embodiments, but it should be understood that these embodiments are merely illustrative of the principles and uses of the present invention. Accordingly, it should be understood that numerous modifications can be made to the exemplary embodiments and other configurations can be devised without departing from the spirit and scope of the invention as defined by the appended claims.

[0148] Furthermore, any number in a range described in the specification or claims, such as representing a characteristic, unit of measurement, condition, physical state, or a particular set of percentages, is intended to be explicitly and literally incorporated herein by reference or otherwise, including any subset of any number within such range. For example, whenever a numerical range having a lower limit RL and an upper limit RU is disclosed, any number R that falls within that range is specifically disclosed. In particular, the following numbers R within the range are specifically disclosed: R=R L +k(R U -R L ), In the formula, k is a variable ranging from 1% to 100% in 1% increments, for example, k is 1%, 2%, 3%, 4%, 5%, .... 50%, 51%, 52%, .... 95%, 96%, 97%, 98%, 99%, or 100%. Furthermore, any numerical range represented by any two values ​​of R calculated above is also specifically disclosed.

Claims

1. A method for producing a supported hydrogenation treatment catalyst, wherein the method is (a) Porous inorganic oxide catalyst carrier or carrier extruder, (i) Boron-containing sources and (ii) an aqueous solution, dispersion, or suspension containing an organic compound or organic chelating agent selected from organic compounds containing at least two oxygen atoms and 2 to 10 carbon atoms, To form a carrier composition containing boron and an organic compound, (b) The composition formed in (a) is calcined, or dried and calcined, to reduce the volatile substance content of the calcined composition to a level of more than 0% to 5% by weight as measured by the loss on ignition (LOI), (c)(b) The calcined composition is impregnated with a solution, dispersion, or suspension containing at least one VIB metal-containing component or source and at least one VIIIIB metal-containing component or source, (d) Including firing the composition formed in step (c) or drying and firing the composition after firing to reduce the volatile substance content of the composition to a level of more than 0% by weight and less than 30% by weight as measured by the loss on ignition (LOI), (1) The amount of boron-containing source is boron B oxide ２ O ３ It is expressed as and is sufficient to form a supporting catalyst having a boron content in the range of 1% to 13% by weight, based on the total weight of the catalyst. (2) Loss on ignition (LOI) is measured by subjecting the weighed sample to an oxygen-containing atmosphere at 1020°F (548.9°C) for 1 hour and measuring the weight loss of the sample. (3) The surface area of ​​the catalyst is in the range of 127 m² / g to 300 m² / g, (4) A method wherein the pore volume of the catalyst is in the range of 0.37 cc / g to 1.0 cc / g.

2. The method according to claim 1, wherein the composition is extruded to form an extruded product.

3. The boron content of the generated support catalyst is boron oxide B ２ O ３ The method according to claim 1 or 2, wherein the amount is expressed as and is in the range of 1.5% to 6% by weight based on the total weight of the catalyst.

4. The boron content of the generated support catalyst is boron oxide B ２ O ３ The method according to any one of claims 1 to 3, wherein the amount is expressed as and is in the range of 2% to 5% by weight based on the total weight of the catalyst.

5. P oxide ２ O ５ The method according to any one of claims 1 to 4, wherein the solution, dispersion, or suspension in step (c) further comprises a phosphorus source, and is expressed as such, and based on the total weight of the catalyst, provides a phosphorus content of the supporting catalyst of 0.5% to 10% by weight.

6. The amount of the phosphorus-containing source is oxide P ２ O ５ which is represented as and provides a phosphorus content of the supported catalyst in the range of 0.5% by weight to 5% by weight or 4% by weight to 10% based on the total weight of the catalyst, according to the method of claim 5.

7. The boron-containing source is metaboric acid (HBO ２ ), ortho-boric acid (H ３ BO ３ ), ammonium borate tetrahydrate [(NH ４ ) 2B ４ O ７ 4H ２ O], sodium tetraborate, ammonium borate, ammonium tetraborate [(NH ４ ) 2B ４ O ７ ], boron oxide (B ２ O ３ The method according to any one of claims 1 to 6, wherein a lithium tetraborate, mono-, di-, or tri-alkylborate amine, ammonium tetraphenylborate, organoboron compounds, and mixtures thereof is selected.

8. The method according to any one of claims 1 to 7, wherein the organic compound or chelate is selected from organic compounds comprising at least two oxygen atoms and 2 to 10 carbon atoms, and ethers, esters, acetals, acid chlorides, acid amides, oligomers, or polymers thereof, and / or (ii) organic compounds comprising at least one covalently bonded nitrogen atom and at least one carbonyl moiety.

9. The method according to any one of claims 1 to 8, wherein the organic compound is selected from acetic acid, citric acid, tartaric acid, oxalic acid, maleic acid, malonic acid, malic acid, butanediol, pyruvaldehyde, glycolaldehyde, acetaldol, tartaric acid, ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, tetrapentylene glycol, polyethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether, and mixtures thereof.

10. The method according to any one of claims 1 to 9, wherein the boron source contains boric acid and the organic compound contains citric acid.

11. The method according to any one of claims 1 to 10, wherein the solution, dispersion, or suspension in step (c) comprises at least one organic chelating agent selected from (i) organic compounds comprising at least two oxygen atoms and 2 to 10 carbon atoms, and ethers, esters, acetals, acid chlorides, acid amides, oligomers, or polymers thereof, and / or (ii) organic compounds comprising at least one covalently bonded nitrogen atom and at least one carbonyl moiety.

12. The method according to claim 11, comprising an organic chelating agent selected from acetic acid, citric acid, oxalic acid, maleic acid, malonic acid, malic acid, ethylene glycol, and ammonium bicarbonate.

13. The method according to any one of claims 1 to 12, wherein the loss on ignition after step (b) is greater than 0 to 2% by weight.

14. The method according to any one of claims 1 to 13, wherein the catalyst exhibits a loss on ignition of 3 to 7% by weight after step (d).

15. The method according to any one of claims 1 to 14, wherein the porous inorganic oxide is selected from eta, theta, or gamma alumina and mixtures thereof, silica, silica-alumina, alumina in which silica-alumina is dispersed, silica-coated alumina, alumina-coated silica, magnesia, zirconia, titania, titania-alumina, and mixtures thereof.

16. A method for producing an inorganic oxide catalyst support, wherein the method is (a) A porous inorganic oxide in the form of fine particles, (1) Boron-containing source and (2) Combining with a composition comprising an aqueous solution, dispersion, or suspension containing an organic compound selected from the group consisting of compounds containing at least two oxygen atoms and 2 to 10 carbon atoms, (b) Extruding the combination in (a) to form an extruded product, (c) Including firing the extruded material to a dryness level of more than 0% by weight to 5% by weight as measured by the loss on ignition (LOI), (i) The boron-containing source is boron B oxide ２ O ３ It is expressed as and present in an amount that provides a boron content in the range of 1% to 13% by weight, based on the total weight of the support. (ii) A method in which the loss on ignition is measured by subjecting the weighed sample to an oxygen-containing atmosphere at 1020°F (548.9°C) for 1 hour and measuring the weight loss.

17. The boron content of the support is B oxide ２ O ３ The method according to claim 16, wherein it is expressed as and is in the range of 1.5% to 6% by weight based on the total weight of the support.

18. The boron content of the catalyst support is B oxide ２ O ３ The method according to claim 17, wherein it is expressed as and is in the range of 2% to 5% by weight based on the total weight of the support.

19. In step (a), (1) The boron-containing source is meta-boric acid (HBO ２ ), ortho-boric acid (H ３ BO ３ ), ammonium borate tetrahydrate [(NH ４ ) 2B ４ O ７ 4H ２ O], sodium tetraborate, ammonium borate, ammonium tetraborate [(NH ４ ) ２ B ４ O ７ ], boron oxide (B ２ O ３ ), selected from lithium tetraborate, mono-, di-, or tri-alkylborate amines, ammonium tetraphenylborate, organoboron compounds, and mixtures thereof, wherein the organic compound contains citric acid. (2) The method according to any one of claims 16 to 18, wherein the organic compound or chelate is selected from organic compounds comprising at least two oxygen atoms and 2 to 10 carbon atoms, and ethers, esters, acetals, acid chlorides, acid amides, oligomers, or polymers thereof, and / or (ii) organic compounds comprising at least one covalently bonded nitrogen atom and at least one carbonyl moiety.

20. The method according to any one of claims 16 to 19, wherein in step (a), the boron-containing source contains boric acid, and the organic compound or chelate contains citric acid.

21. The method according to any one of claims 16 to 20, wherein the porous inorganic oxide is selected from eta, theta, or gamma alumina and mixtures thereof, silica, silica-alumina, alumina in which silica-alumina is dispersed, silica-coated alumina, alumina-coated silica, magnesia, zirconia, titania, titania-alumina, and mixtures thereof.

22. A supported hydrogenation treatment catalyst, A porous inorganic oxide catalyst support or catalyst support, At least one VIB group metal component in the form of an oxide, At least one group VIIIB metal component in the form of an oxide, B ２ O ３ It contains a boron-containing component in the form of an oxide, which is represented as (a) The content of boron oxide is in the range of 1 to 13% by weight, based on the total weight of the catalyst. (b) If present, the phosphorus component content is at least 0.5% by weight based on the total weight of the catalyst. (1) The VIB and VIIIB metal components, as well as the phosphorus and boron components, are supported on and / or in a support or carrier containing alumina or silica in the form of a pill having an internal cross-section and an external surface, (2) The position crossing the internal cross section of the pill is identified by the percentage of the distance along the center line from the first edge of the pill cross section, referred to as the starting point or 0%, to the furthest edge of the pill cross section, referred to as 100%, (I) The concentration of the VIB group metal oxide in the first 33 1 / 3% or the last 33 1 / 3% of the pill cross section is 20% to 100% higher than the concentration of the VIB group metal oxide in the central 33 1 / 3% of the pill cross section. (II) A supported hydrogenation catalyst in which the concentrations of the Group VIB and Group VIIIB metal oxide components, and, if present, the phosphorus oxide component, are determined by electron probe trace analysis, extending across the cross-section of the pill to the outer surface.

23. The catalyst according to claim 22, wherein the catalyst comprises a phosphorus component in the form of an oxide represented as P2O5.

24. The catalyst according to claim 22 or 23, wherein the VIB group metal component is selected from molybdenum, tungsten, or chromium oxides.

25. The catalyst according to any one of claims 22 to 24, wherein the group VIIIB metal component is selected from cobalt or nickel oxide.

26. The catalyst according to any one of claims 22 to 25, wherein the VIB group metal component comprises molybdenum or tungsten.

27. A catalyst according to any one of claims 22 to 26, comprising phosphorus.

28. The catalyst according to claim 27, wherein the concentration of phosphorus oxide in the first 33 1 / 3% or the last 33 1 / 3% of the pill cross section is 30% to 350% higher than the concentration of phosphorus oxide in the central 33 1 / 3% of the pill cross section.

29. The amount of the phosphorus component is, ２ O ５ The catalyst according to claim 27 or 28, which is expressed as and is in the range of 4% to 10% by weight based on the total weight of the catalyst.

30. The catalyst according to claim 29, wherein the amount of the phosphorus component is in the range of 4% by weight to 7% by weight.

31. Oxide B ２ O ３ The catalyst according to claim 30, wherein the boron content is in the range of 2% to 8% by weight, based on the total weight of the catalyst.

32. The catalyst according to claim 31, wherein the boron content is in the range of 4% by weight to 6% by weight.

33. The catalyst according to any one of claims 22 to 32, wherein the carrier comprises alumina.

34. The catalyst according to any one of claims 22 to 33, wherein the boron source contains boric acid.

35. The catalyst according to any one of claims 22 to 34, further comprising an organic additive.

36. The aforementioned organic additive The catalyst according to claim 35, selected from (i) organic compounds comprising at least two oxygen atoms and 2 to 10 carbon atoms, and ethers, esters, acetals, acid chlorides, acid amides, oligomers, or polymers thereof, and / or (ii) organic compounds comprising at least one covalently bonded nitrogen atom and at least one carbonyl moiety.

37. The catalyst according to any one of claims 1 to 36, wherein the porous inorganic oxide is selected from eta, theta, or gamma alumina and mixtures thereof, silica, silica-alumina, alumina in which silica-alumina is dispersed, silica-coated alumina, alumina-coated silica, magnesia, zirconia, titania, titania-alumina, and mixtures thereof.

38. A method comprising hydrogenating a hydrocarbon feed by contacting the hydrocarbon feed with a supported hydrogenation catalyst according to any one of claims 22 to 37 under hydrogenation conditions.

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