Hydrotreating catalyst carrier compositions, methods for production thereof, and uses thereof

Abstract

A method for preparing a modified alumina powder, that includes alumina, titanium, and phosphorus, includes providing an aqueous solution of aluminum sulfate; adding a titanium compound and a phosphorus compound to the aqueous solution of aluminum sulfate to provide a mixture; contacting the mixture with an aqueous solution comprising a base precipitation agent to provide a precipitate; isolating the precipitate as an isolated precipitate; and drying the precipitate to provide the modified alumina powder.

Description

Atty. Dkt. No.: 114096-5135 (W10340-00) HYDROTREATING CATALYST CARRIER COMPOSITIONS, METHODS FOR PRODUCTION THEREOF, AND USES THEREOF FIELD

[0001] The present technology is generally related hydrotreating catalyst carrier compositions, methods for production thereof, and uses thereof. Specifically, the technology is related to pseudo-boehmite alumina containing titanium and phosphorous that is prepared by co-precipitating alumina with a titanium compound and a phosphorus compound. BACKGROUND

[0002] Increasing regulatory and operational pressure has resulted in the need for hydrocarbons that have low sulfur levels and nitrogen levels. Hydroprocessing, which involves treating a hydrocarbon with hydrogen in the presence of a catalyst, is a conventional method for heteroatom (e.g., sulfur and nitrogen) removal. A variety of investigations have been hitherto made in relation to the hydrorefining catalyst and carriers, for example to improve the ability to remove the heteroelements. SUMMARY

[0003] Provided in one aspect is a method for preparing a modified alumina powder comprising alumina, titanium, and phosphorus, the method comprising: providing an aqueous solution of aluminum sulfate; adding a titanium compound and a phosphorus compound to the aqueous solution of aluminum sulfate to provide a mixture; contacting the mixture with an aqueous solution comprising a base precipitation agent to provide a precipitate; isolating the precipitate as an isolated precipitate; and drying the precipitate to provide the modified alumina powder.Atty. Dkt. No.: 114096-5135 (W10340-00)

[0004] In some embodiments, the titanium compound is titanyl sulfate, titanium tetrachloride, titanium oxysulfate, titanium oxychloride, titanium dioxide, or a mixture of any two or more thereof.

[0005] In some embodiments, the phosphorus compound is phosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid and tetraphosphoric acid, or a mixture of any two or more thereof.

[0006] In some embodiments, the base precipitation agent is sodium aluminate, sodium hydroxide, sodium carbonate, or a mixture of any two or more thereof.

[0007] In some embodiments, the precipitate is formed at a pH of about 7.5 to about 10.0. In some embodiments, the precipitate is formed at a temperature of about 125 °F (about 52 °C) to about 155 °F (about 68 °C). In some embodiments, the isolated precipitate is washed and / or filtered prior to drying.

[0008] In some embodiments, the amount of titanium present in the modified alumina powder, measured as TiO2, is about 0.1 wt% to about 5 wt% or about 0.3 wt% to about 4.5 wt%, based on the total weight of the modified alumina powder.

[0009] In some embodiments, the amount of phosphorus present in the modified alumina powder, measured as P2O5, is about 0.1 wt% to about 5% wt% or about 0.1 wt% to about 4.0 wt%, based on the total weight of the modified alumina powder.

[0010] Provided in one aspect is a method for preparing a catalyst carrier, the method comprising: providing any one of the modified alumina powder prepared in accordance with this disclosure; treating the modified alumina powder with a peptizing agent to provide a peptized alumina powder; and extruding the peptized alumina to provide extrudates; drying the extrudates to form dried extrudates; and calcining the dried extrudates to provide the catalyst carrier.Atty. Dkt. No.: 114096-5135 (W10340-00)

[0011] In some embodiments, the catalyst carrier supports a catalytically active metal suitable for the hydrodesulfurization of hydrocarbon feedstocks. In some embodiments, the catalyst carrier supports a catalytically active metal suitable for the hydrodenitrogenation of hydrocarbon feedstocks.

[0012] In some embodiments, the peptizing agent is nitric acid, hydrochloric acid, formic acid, acetic acid, propionic acid, ammonium hydroxide, or a mixture of any two or more thereof.

[0013] In some embodiments, the modified alumina powder comprises titanium, measured as TiO2, at about 1.8 wt% to about 3.8 wt%, based on total weight of the modified alumina powder.

[0014] In some embodiments, the modified alumina powder comprises phosphorus, measured as P2O5, at about 0.8 wt% to about 1.8 wt%, based on total weight of the modified alumina powder.

[0015] In some embodiments, the catalyst carrier has a surface area of about 150 to about 300 m2 / g. In some embodiments, the catalyst carrier has a pore volume with respect to pores having a pore diameter of 20 to 600 Å, of about 0.5 to about 1.0 cc / g. In some embodiments, the catalyst carrier has at least about 60% of the total pore volume is in the pores having a diameter between about 70 Å about 130 Å, as determined by nitrogen porosimetry. In some embodiments, the catalyst carrier has less than about 5% of the total pore volume in pores having a diameter about 300 Å, as determined by nitrogen porosimetry. In some embodiments, the catalyst carrier has less than about 3% of the total pore volume in pores having a diameter about 1000 Å, as determined by mercury porosimetry.

[0016] Provided in one aspect is a method for preparing a catalyst for hydrodesulfurization or hydrodenitrogenation of hydrocarbon feedstocks, the method comprising: impregnating any one of the catalyst carriers described herein with an aqueous solution to form an impregnated catalyst carrier;Atty. Dkt. No.: 114096-5135 (W10340-00) wherein the aqueous solution comprises at least one catalytic agent or catalytic agent precursor comprising chromium, molybdenum, tungsten, cobalt, rhodium, iridium, nickel, platinum, palladium, or a combination of any two or more thereof, and phosphorus.

[0017] In some embodiments, the at least one catalytic agent comprises cobalt, nickel, molybdenum, or a combination of any two or more thereof.

[0018] Provided in one aspect is a modified alumina powder used as a material for preparing a catalyst carrier comprising, the modified alumina powder comprising: alumina; about 0.1 wt% to about 5 wt% titanium, measured as TiO2, based on the total weight of the modified alumina powder; and about 0.1 wt% to about 5 wt% phosphorus, measured as P2O5, based on the total weight of the modified alumina powder. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] FIG.1 is a schematic depiction of the preparation of a pseudo-boehmite alumina containing titanium and phosphorous was prepared via co-precipitating alumina with the presence of a titanium compound and a phosphorus compound, according to an illustrative embodiment. DETAILED DESCRIPTION

[0020] Various embodiments are described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced with any other embodiment(s).

[0021] As used herein, “about” will be understood by persons of ordinary skill in the art and will vary to some extent depending upon the context in which it is used. If there areAtty. Dkt. No.: 114096-5135 (W10340-00) uses of the term which are not clear to persons of ordinary skill in the art, given the context in which it is used, “about” will mean up to plus or minus 10% of the particular term.

[0022] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.

[0023] Described herein are pseudo-boehmite alumina containing titanium and phosphorous was prepared via co-precipitating alumina with the presence of a titanium compound and a phosphorus compound. These alumina carriers are referred as Ti-Phos- alumina (TiP-alumina). The introduction of additives did not result in the loss of surface area or pore volume, and the alumina carriers described herein have similar properties to alumina carriers without any additives. Also, as demonstrated herein, the hydro-processing catalysts made TiP-alumina described herein have improved activities in hydrodesulfurization and hydrodenitrogenation.

[0024] FIG.1 is a schematic depiction of the preparation of pseudo-boehmite alumina containing titanium and phosphorous was prepared via co-precipitating alumina with the presence of a titanium compound and a phosphorus compound.

[0025] In one aspect, a method is provided for preparing a modified alumina powder that includes alumina, titanium, and phosphorus. The methods include providing an aqueous solution of aluminum sulfate, adding a titanium compound and a phosphorus compound to the aqueous solution of aluminum sulfate to provide a mixture, contacting the mixture withAtty. Dkt. No.: 114096-5135 (W10340-00) an aqueous solution that includes a base precipitation agent to provide a precipitate, isolating the precipitate as an isolated precipitate, and drying the precipitate to provide the modified alumina powder. The titanium compound may be a titanyl sulfate, titanium tetrachloride, titanium oxysulfate, titanium oxychloride, titanium dioxide, or a mixture of any two or more thereof. In some embodiments, the titanium compound is titanyl sulfate. The phosphorus compound may be phosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid and tetraphosphoric acid, or a mixture of any two or more thereof. In some embodiments, the phosphorus compound is phosphoric acid. In other embodiments, the phosphorus compound is orthophosphoric acid. The base precipitation agent may be sodium aluminate, sodium hydroxide, sodium carbonate, or a mixture of any two or more thereof. In some embodiments, the base precipitation agent is sodium aluminate.

[0026] The precipitate may be formed at a pH of about 7.5 to about 10.0. This includes pH values and ranges of about 7.5, about 8.0, about 8.5, about 9.0, about 9.5, and about 10.0. In some embodiments, the precipitate is formed at a pH of about 8.5 to about 9.5.

[0027] The precipitate may be formed at a temperature that is not higher than about 212 °F (about 100 °C) and no lower than about ambient temperature. The precipitate may be formed at a temperature of about 125 °F (about 52 °C) to about 155 °F (about 68 °C). This includes temperature values of about 125 °F (about 52 °C), about 130 °F (about 54 °C), about 135 °F (about 57 °C), about 140 °F (about 60 °C), about 145 °F (about 63 °C), about 150 °F (about 66 °C), and 155 °F (about 68 °C).

[0028] The methods may also include washing and / or filtering the isolated precipitate prior to drying.

[0029] The amount of titanium present in the modified alumina powder, measured as TiO2, is less than about 5 wt%, based on the total weight of the modified alumina powder. In some embodiments, the amount of titanium present in the modified alumina powder, measured as TiO2, is about 0.1 wt% to about 5 wt%, based on the total weight of the modified alumina powder. In some embodiments, the amount of titanium present in the modified alumina powder, measured as TiO2, is about 0.3 wt% to about 4.5 wt%, based on the total weight of the modified alumina powder, including about 0.3 wt%, about 0.4 wt%,Atty. Dkt. No.: 114096-5135 (W10340-00) about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, and 4 wt%.

[0030] In some embodiments, the amount of phosphorus present in the modified alumina powder, measured as P2O5, is about 0.1 wt% to about 5.0 wt%, based on the total weight of the modified alumina powder. In some embodiments, the amount of phosphorus present in the modified alumina powder, measured as P2O5, is about 0.1 wt% to about 4.0 wt%, based on the total weight of the modified alumina powder, including about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, and 4 wt%.

[0031] In another aspect, the methods include preparing a catalyst carrier. Such methods may include providing the modified alumina powder prepared according to the embodiments above, treating the modified alumina powder with a peptizing agent to provide a peptized alumina powder, extruding the peptized alumina to provide extrudates, drying the extrudates to form dried extrudates, and calcining the dried extrudates to provide the catalyst carrier.

[0032] The catalyst carrier may support a catalytically active metal suitable for the hydrodesulfurization of hydrocarbon feedstocks. In some embodiments, the catalyst carrier supports a catalytically active metal suitable for the hydrodenitrogenation of hydrocarbon feedstocks.

[0033] The peptizing agent of the methods may be nitric acid, hydrochloric acid, formic acid, acetic acid, propionic acid, ammonium hydroxide, or a mixture of any two or more thereof. In some embodiments, the peptizing agent is nitric acid,

[0034] A variety of shaping methods may be employed for shaping the catalysts. Illustrative shapes, include, for example, clover shapes, cylindrical shapes, cylinder shapes, and spherical shapes. In some embodiments, the extrudates are quadrilobed extrudates.

[0035] Drying may be conducted at a temperature of no lower than about 200 ⁰F (about 90 ⁰C). In some embodiments, drying is conducted at a temperature of from about 200Atty. Dkt. No.: 114096-5135 (W10340-00) ⁰F to about 400 ⁰F (about 90 ⁰C to about 205 ⁰C), including about 200 ⁰F, about 250 ⁰F, about 300 ⁰F, about 350 ⁰F, and about 400 ⁰F, for a suitable period of time. The suitable period of time for drying is no shorter than about 1 hour, including from about 1 hour to about 16 hours. In some embodiments, the suitable period of time is about 8 to about 16 hours, including 8, 9, 10, 11, 12, 13, 14, 15, and 16 hours. In some embodiments, the drying is conducted at a temperature of about 200 ⁰F to about 400 ⁰F (about 90 ⁰C to about 205 ⁰C), for a period of about 8 to about 16 hours. The drying is conducted at a suitable temperature for a suitable period of time to provide a total amount of volatiles of less than about 35 wt%.

[0036] Calcining may be conducted at a temperature of about 1000 ⁰F to about 1800 ⁰F (about 535 ⁰C to about 980 ⁰C). This may include temperatures of about 1000 ⁰F, about 1100 ⁰F, about 1200 ⁰F, about 1300 ⁰F, about 1400 ⁰F, about 1500 ⁰F, about 1600 ⁰F, about 1700 ⁰F, and about 1800 °F, for a suitable period of time. In some embodiments, the suitable period of time is about 1 to about 4 hours, including 1, 2, 3, and 4 hours. In some embodiments, the calcining is conducted at a temperature of about 1000 ⁰F to about 1800 ⁰F (about 535 ⁰C to about 980 ⁰C) for a period of about 1 to about 4 hours.

[0037] The modified alumina powder may include titanium, measured as TiO2, at about 1.8 to about 3.8 wt%, based on total weight of the modified alumina powder. This may include about 1.8 wt%, about 1.9 wt%, about 2.0 wt%, about 2.1 wt%, about 2.2 wt%, about 2.3 wt%, about 2.4 wt%, about 2.5 wt%, about 2.6 wt%, about 2.7 wt%, about 2.8 wt%, about 2.9 wt%, about 3.0 wt%, about 3.1 wt%, about 3.2 wt%, about 3.3 wt%, about 3.4 wt%, about 3.5 wt%, about 3.6 wt%, about 3.7 wt%, or about 3.8 wt%,

[0038] The modified alumina powder may include phosphorus, measured as P2O5, at about 0.8 to about 1.8 wt%, based on total weight of the modified alumina powder. This may include about 0.8 wt%, about 0.9 wt%, about 1.0 wt%, about 1.1 wt%, about 1.2 wt%, about 1.3 wt%, about 1.4 wt%, about 1.5 wt%, about 1.6 wt%, about 1.7 wt%, or 1.8 wt%.

[0039] As demonstrated in the Examples, the addition of a titanium compound and a phosphorus compound does change the pore volume or surface area of the modified alumina as compared to unmodified alumina. The catalyst carriers described herein possess specific properties of surface area, pore volume and pore volume distribution.Atty. Dkt. No.: 114096-5135 (W10340-00)

[0040] Surface area as defined herein is determined by BET surface area analysis. The BET method of measuring surface area has been described in detail by Brunauer, Emmett and Teller in J. Am. Chem. Soc.60 (1938) 309-319, which is incorporated herein by reference. In some embodiments, the catalyst carrier has a surface area of about 150 to about 300 m2 / g. This may include about 150, about 155, about 160, about 165, about 170, about 175, about 180, about 185, about 190, about 195, about 200, about 205, about 210, about 215, about 220, about 225, about 230, about 235, about 240, about 245, about 250, about 255, about 260, about 265, about 270, about 275, about 280, about 285, about 290, about 295, or about 300 m2 / g.

[0041] The pore volume(s) are recited herein may be measured using nitrogen porosimetry and / or mercury penetration porosimetry. Typically, pores having a diameter of 1000 A or less are measured using nitrogen porosimetry, while pores having a diameter of greater than 1000 A are measured using mercury penetration porosimetry.

[0042] Pore volume is the volume of a liquid which is adsorbed into the pore structure of the sample at saturation vapor pressure, assuming that the adsorbed liquid has the same density as the bulk density of the liquid. The liquid used for nitrogen porosimetry is liquid nitrogen. The procedure for measuring pore volumes by nitrogen physisorption is as disclosed and described in D. H. Everett and F. S. Stone, Proceedings of the Tenth Symposium of the Colstom Research Society, Bristol, England: Academic Press, March 1958, pp.109-110.

[0043] The mercury measurement of the pore volume and the pore size distribution of the alumina carrier material may be determined using any suitable mercury porosimeter capable of a pressure range of atmospheric pressure to about 4200 bar, with a contact angle, Θ = 130°, and a mercury surface tension of 0.49 N / m at room temperature.

[0044] In some embodiments, the catalyst carrier has a pore volume with respect to pores having a pore diameter of 20 to 600 Å, of about 0.5 to about 1.0 cc / g, including about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, and about 1.0 cc / g.Atty. Dkt. No.: 114096-5135 (W10340-00)

[0045] In some embodiments, the catalyst carrier has at least about 60% of the total pore volume is in the pores having a diameter between about 70 Å about 130 Å, as determined by nitrogen porosimetry.

[0046] In some embodiments the catalyst carrier has less than about 5% of the total pore volume in pores having a diameter about 300 Å, as determined by nitrogen porosimetry.

[0047] In some embodiments, the catalyst carrier has less than about 3% of the total pore volume in pores having a diameter about 1000 Å, as determined by mercury porosimetry.

[0048] In a further aspect, a method for preparing a catalyst for hydrodesulfurization or hydrodenitrogenation of hydrocarbon feedstocks is described. The method(s) include impregnating any one of the catalyst carrier described herein with an aqueous solution to form an impregnated catalyst carrier, where the aqueous solution includes at least one catalytic agent or catalytic agent precursor that includes chromium, molybdenum, tungsten, cobalt, rhodium, iridium, nickel, platinum, palladium, or a combination of any two or more thereof, and phosphorus.

[0049] In some embodiments, the at least one catalytic agent includes cobalt, nickel, molybdenum, or a combination of any two or more thereof.

[0050] Such methods may further include aging the impregnated catalyst carrier for a period of about 0.5 to about 2 hours, drying the impregnated catalyst carrier to remove water; and calcining the impregnated catalyst carrier at a temperature of 900 to about 1200 °F (about 480 to about 650 °C) for a period of about 1 to about 2 hours.

[0051] Provided in one aspect is a modified alumina powder used as a material for preparing a catalyst carrier comprising, the modified alumina powder comprising: alumina; about 0.1 wt% to about 5 wt% titanium, measured as TiO2, based on the total weight of the modified alumina powder; and about 0.1 wt% to about 5 wt% phosphorus, measured as P2O5, based on the total weight of the modified alumina powder.Atty. Dkt. No.: 114096-5135 (W10340-00)

[0052] The present invention, thus generally described, will be understood more readily by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present invention. EXAMPLES

[0053] Example 1. Preparation of Co-precipitated TiP-Alumina. This example illustrates the preparation of a co-precipitated TiP-alumina according to an illustrative embodiment of this disclosure.

[0054] An aluminum sulfate solution containing 7 wt% Al2O3was mixed with a titanyl sulfate solution containing 9.5% TiO2 and 75% phosphoric acid to form an acidic solution. The acidic solution contained 3.76 wt% aluminum, 0.32 wt% titanium, and 0.05 wt% phosphorus. A sodium aluminate solution containing 25 wt% Al2O3 was used as the basic solution. A heel of 263 gallons (996 kg) of water was placed in a strike tank. The heel was heated up to 130°F (54°C) with the agitator on. The acidic solution was heated up to 95°F (35°C) and the basic solution was heated up to 100°F (38°C). The feeding flows of both acidic and basic solutions was simultaneously started. The feeding flow rate of the acidic solution was set to be 3.6 gallon per minute and the flow rate of the basic solution was adjusted as needed to maintain the pH of the reaction mixture at 8.8. The strike temperature was maintained at 130°F (54°C). The strike was stopped after 22 min. The total usage of the acidic solution was about 79 gallons and that of the basic solution was about 49 gallons.

[0055] The reaction mixture was filtered to obtain the co-precipitated TiP-alumina wet mix, which was subsequently washed on the filter belt to remove residual sodium and sulfate. The resulting filter cake was then spray dried to obtain a TiP-alumina powder containing from 1.87 wt% TiO2 and 0.91% P2O5.

[0056] Example 2. Preparation of Extrudate Catalyst Carrier. 600 g of the TiP- alumina obtained from Example 1 with a total volatiles of 23.7-24.4 wt% was mixed with 25.7 g of concentrated nitic acid (70 wt%) and 1008-1017 g of water for 40 min to provide a wet mix. The wet mix was extruded using a extruder into asymmetrical quadrilobed shaped extrudates (nominal diameter 0.05 inch). The extrudates were dried at 250°F (121°C) for 2Atty. Dkt. No.: 114096-5135 (W10340-00) hours and 400 °F (204 °C) for two more hours before being calcined at 1400 ⁰F (760 ⁰C) for 1 hour in 2 liter / min air flow.

[0057] The obtained extrudate catalyst carrier had a surface area of 257-267 m2 / g and a pore volume of 0.79-0.80 cm3 / g.

[0058] Example 3. Preparation of Catalyst. 50 g of volatiles-free TiP-alumina base obtained from Example 2 was impregnated using the incipient wetness method by aqueous metal solution. The aqueous solution was prepared by using molybdenum trioxide, nickel carbonate, and phosphoric acid, and contained 14.4%-15.5% Mo, 3.2%-3.4% Ni, and 0.6%- 2.6% P. The impregnated base was dried and calcined at 950 ⁰F (510 ⁰C) to obtain the final catalyst (Cat A or B). The properties of the catalyst prepared in these examples is shown in the below table. Chemical composites Physical PropertiesCat Catalyst Carrier Mo Ni P Ti SA PD g / cc

[0059] Example 4: HDS (hydrodesulfurization), HDMCR (hydrotreating catalyst for microcarbon reduction), and HDN (hydrodenitrogenation) Performance.

[0060] Catalysts in accordance with the disclosure herein were evaluated under representative resid hydrotreating conditions for the conversion of sulfur (HDS), carbon residue (HDMCR), and nitrogen (HDN). After being presulfided using dimethyl disulfide, the tested catalysts were contacted with a Middle Eastern-derived residuum feed in a fixed- bed flow reactor at identical reactor pressure, temperature and LHSV. The relative rates for HDS, HDMCR and HDN were used to compare the activity of the tested catalysts.Atty. Dkt. No.: 114096-5135 (W10340-00)

[0061] The below summarize HDS, HDMCR and HDN activities of the TiP-Alumina prepared in accordance with the Examples, which show improved activities as compared to alumina carrier that does not contain both titanium and phosphorus. Relative Rate ConstantsCat Catalyst Carrier HDS HDMCR HDN

[0062] The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,” etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase “consisting essentially of” will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of” excludes any element not specified.

[0063] The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and compositions within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within theAtty. Dkt. No.: 114096-5135 (W10340-00) scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds, or compositions, which can of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0064] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0065] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.

[0066] All publications, patent applications, issued patents, and other documents referred to in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.

[0067] While certain embodiments have been illustrated and described, it should be understood that changes and modifications can be made therein in accordance with ordinaryAtty. Dkt. No.: 114096-5135 (W10340-00) skill in the art without departing from the technology in its broader aspects as defined in the following claims.

Claims

Atty. Dkt. No.: 114096-5135 (W10340-00) WHAT IS CLAIMED IS:

1. A method for preparing a modified alumina powder comprising alumina, titanium, and phosphorus, the method comprising: providing an aqueous solution of aluminum sulfate; adding a titanium compound and a phosphorus compound to the aqueous solution of aluminum sulfate to provide a mixture; contacting the mixture with an aqueous solution comprising a base precipitation agent to provide a precipitate; isolating the precipitate as an isolated precipitate; and drying the precipitate to provide the modified alumina powder.

2. The method of claim 1, wherein the titanium compound is titanyl sulfate, titanium tetrachloride, titanium oxysulfate, titanium oxychloride, titanium dioxide, or a mixture of any two or more thereof.

3. The method of claim 1 or 2, wherein the phosphorus compound is phosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid and tetraphosphoric acid, or a mixture of any two or more thereof.

4. The method of any one of claims 1-3, wherein the base precipitation agent is sodium aluminate, sodium hydroxide, sodium carbonate, or a mixture of any two or more thereof.

5. The method of any one of claims 1-4, wherein the precipitate is formed at a pH of about 7.5 to about 10.0 and / or the precipitate is formed at a temperature of about 125 °F (about 52 °C) to about 155 °F (about 68 °C).

6. The method of any one of claims 1-5, wherein the isolated precipitate is washed and / or filtered prior to drying.

7. The method of any one of claims 1-6, wherein the amount of titanium present in the modified alumina powder, measured as TiO2, is about 0.1 wt% to about 5 wt% orAtty. Dkt. No.: 114096-5135 (W10340-00) about 0.3 wt% to about 4.5 wt%, based on the total weight of the modified alumina powder.

8. The method of any one of claims 1-7, wherein the amount of phosphorus present in the modified alumina powder, measured as P2O5, is about 0.1 wt% to about 5% wt% or about 0.1 wt% to about 4.0 wt%, based on the total weight of the modified alumina powder.

9. A method for preparing a catalyst carrier, the method comprising: providing the modified alumina powder prepared according to of any one of claims 1- 8; treating the modified alumina powder with a peptizing agent to provide a peptized alumina powder; and extruding the peptized alumina to provide extrudates; drying the extrudates to form dried extrudates; and calcining the dried extrudates to provide the catalyst carrier.

10. The method of claim 9, wherein the catalyst carrier supports a catalytically active metal suitable for the hydrodesulfurization of hydrocarbon feedstocks.

11. The method of claims 9 or 10, wherein the catalyst carrier supports a catalytically active metal suitable for the hydrodenitrogenation of hydrocarbon feedstocks.

12. The method of any one of claims 9-11, wherein the peptizing agent is nitric acid, hydrochloric acid, formic acid, acetic acid, propionic acid, ammonium hydroxide, or a mixture of any two or more thereof.

13. The method of any one of claims 9-12, wherein the modified alumina powder comprises titanium, measured as TiO2, at about 1.8 wt% to about 3.8 wt%, based on total weight of the modified alumina powder.

14. The method of any one of claims 9-13, wherein the modified alumina powder comprises phosphorus, measured as P2O5, at about 0.8 wt% to about 1.8 wt%, based on total weight of the modified alumina powder.Atty. Dkt. No.: 114096-5135 (W10340-00) 15. The method of any one of claims 9-14, wherein the catalyst carrier has a surface area of about 150 to about 300 m2 / g.

16. The method of any one of claims 9-15, wherein the catalyst carrier has a pore volume with respect to pores having a pore diameter of 20 to 600 Å, of about 0.5 to about 1.0 cc / g.

17. The method of any one of claims 9-16, wherein the catalyst carrier has at least about 60% of the total pore volume is in the pores having a diameter between about 70 Å about 130 Å, as determined by nitrogen porosimetry.

18. The method of any one of claims 9-17, wherein the catalyst carrier has less than about 5% of the total pore volume in pores having a diameter about 300 Å, as determined by nitrogen porosimetry.

19. The method of any one of claims 9-18, wherein the catalyst carrier has less than about 3% of the total pore volume in pores having a diameter about 1000 Å, as determined by mercury porosimetry.

20. A method for preparing a catalyst for hydrodesulfurization or hydrodenitrogenation of hydrocarbon feedstocks, the method comprising: impregnating the catalyst carrier prepared in accordance with any one of claims 9-19 with an aqueous solution to form an impregnated catalyst carrier; wherein the aqueous solution comprises at least one catalytic agent or catalytic agent precursor comprising chromium, molybdenum, tungsten, cobalt, rhodium, iridium, nickel, platinum, palladium, or a combination of any two or more thereof, and phosphorus.

21. The method of claim 20, wherein the at least one catalytic agent comprises cobalt, nickel, molybdenum, or a combination of any two or more thereof.

22. A modified alumina powder prepared by the method of any one of claims 1-8.

23. A catalyst carrier prepared by the method of any one of claims 9-19.Atty. Dkt. No.: 114096-5135 (W10340-00) 24. A catalyst prepared by the method of any one of claims 20-21.

25. A modified alumina powder used as a material for preparing a catalyst carrier comprising, the modified alumina powder comprising: alumina; about 0.1 wt% to about 5 wt% titanium, measured as TiO2, based on the total weight of the modified alumina powder; and about 0.1 wt% to about 5 wt% phosphorus, measured as P2O5, based on the total weight of the modified alumina powder.

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