TW201130739A - Process for making boehmite alumina, and methods for making catalysts using the same - Google Patents

Abstract

This invention comprises a novel process for making boehmite alumina and comprises selecting an alumina, and heating it in the presence of an alkali metal hydroxide concentration of at least 0.2 mole per mole of the selected alumina. The heating is conducted at a temperature of at least 100 DEG C and preferably carried out under steam in an autoclave. The boehmite alumina recovered from this process is particularly suitable as active matrix in catalysts used in hydrocarbon conversion processes, especially fluidized catalyst cracking processes for converting hydrocarbon feedstock into gasoline and other petroleum products.

Description

201130739 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to boehmite alumina and a method of manufacturing the same. The present invention is also directed to a process for producing a catalyst from boehmite alumina, particularly a particulate catalyst suitable for use in a fluid catalytic cracking process. [Prior Art] Boehmite bauxite, also known as α-gibbsite, is an alumina hydroxide material often used in the industry. These materials are used to make ceramics, honing abrasives, flame retardants, adsorbents, catalysts, and materials in composite materials. Commercial boehmite bauxite is primarily used for catalytic applications, such as cracking catalysts, particularly for fluidized bed catalytic cracking (FCC) processes. The alumina itself is catalytically active but generally combines with other catalytically active materials to form the final catalyst. Zeolites are often used as the primary catalytic species in cracking catalysts. The final form of the cracking catalyst will vary, but regardless of its morphology, 'boehmite bauxite will generally affect the performance of the catalyst during the cracking process. Boehmite is most often obtained by alkalizing or acidifying an aluminate to neutralize aluminum salts, hydrolysis of aluminum alkoxides, reaction of aluminum metal with water (amalgamation), and rapid calcination of gibbsite. It is produced by a method such as rehydration of amorphous p-alumina. The p Η値 and temperature of the suspension during the ripening of the above process will affect the final properties of the boehmite produced. For example, the rate of crystallization increases with increasing ρ Η値 and temperature. See U.S. Patent Application 2,7/〇2,749,3. The '903 patent application describes the manufacture of boehmite bauxite by aging and/or processing boehmite alumina precursors under hydrothermal conditions. Reference may also be made to the '891 patent application of US 2008/003 1 808, US 6,55 5,496, and US 2 0 0 6 / 0 0 9 6 8 9 to add a pH adjusting agent in the above-mentioned ripening step, For example potassium hydroxide and/or sodium. The '903 patent application also teaches the addition of sodium hydroxide, apparently to control the type of crystalline product produced. The '903 patent, for example, is directed to the manufacture of quasi-crystalline boehmite, so the pH of the slurry is adjusted, and the amount of pH adjuster is selected to facilitate the preparation of quasi-crystalline boehmite, which is microcrystalline. The opposite is the bohemian stone. An example of the '903 patent is to regulate pH by increasing the pH by first adding an acid and then adding a base to increase the pH. However, alkali metals are believed to be most likely to form salts with the anions of the added acid, and therefore any excess alkali metal will only result in an alkali metal hydroxide concentration of about 0.02 moles per mole of alumina. See Example 10 below. As previously mentioned, alumina is often used to make cracking catalysts, particularly FCC catalysts. In addition to providing the final catalyst volume and surface area, alumina is also an active component of the catalyst. Therefore, alumina is not only a product that can positively affect the FCC process, including gasoline fractions, which can also have deleterious effects on other parameters in the process, such as hydrogen generation and hydrocarbon residues deposited on the catalyst ( The amount of coke), on the other hand, reduces the yield of available products. Therefore, it is hoped that a balanced development and utilization of bauxite will have a favorable effect on these properties. -4 - 201130739 SUMMARY OF THE INVENTION The present invention comprises the production of boehmite by heating alumina in the presence of an alkali metal hydroxide, the alkali metal hydroxide having a higher concentration than previously controlled by alkali The concentration that the additive can reach. More specifically, the method comprises: a method of making boehmite alumina, the method comprising: (a) selecting alumina, (b) placing the alumina in a medium that heats it, (c) in the base a bar having a metal hydroxide concentration of at least 0.20 mol/mole bauxite, heating the bauxite at a temperature of 1 ° C or higher, and (d) recovering from the medium after heating Stone bauxite. The heating is usually carried out at a temperature ranging from 1 Torr to 300 ° C, preferably in the presence of steam, for example, in a vacuum vessel. When the present invention is used, the alumina is generally treated in the range of an alkali metal hydroxide concentration of from 0.2 to 2.20 moles per mole of alumina. The boehmite alumina prepared according to the above method has proven to be particularly suitable for the production of catalysts, especially for fluid catalytic cracking (FCC) processes. Accordingly, the present invention also includes a method for producing a catalyst, wherein the method comprises: (a) selecting alumina, (b) placing the alumina in a medium in which it is heated, (c) in an alkali metal hydroxide concentration Heating the selected alumina at a temperature of 100 ° C or higher with a condition of at least 0.20 mol/mole bauxite

-5- S 201130739 (d) After heating, the boehmite bauxite is recovered from the medium, (e) the recovered bauxite is combined with the catalytic material or material, and (0 will be recovered from the bauxite and the catalytic material or material (different) The combination of recycled boehmite and alumina is processed into a finished product form. When the catalytic material and/or material is treated together with the inventive soil to produce a finished catalyst product, one or more optional materials may be included in (e), Such as a matrix, a binder and/or a functional additive. The catalytic material for the FCC catalyst generally comprises a zeolite, and the final FCC catalyst is typically a microparticle having an average particle size in the range of 20 to 150 microns. "There is a general well-known meaning in the refining catalyst industry and other industries." It refers to an alumina hydrate that exhibits an X-ray diffraction (XRD) pattern close to that of aluminum hydroxide [AIO(OH)]. Mullite contains a wide range of alumina hydrates. These alumina hydrates have different surface areas, pore volumes, specific densities, and exhibit different thermal characteristics during heat treatment. These materials exhibit characteristic peaks of boehmite [AIO(OH)] but the width and position of these peaks may vary in the pattern. The sharpness of the XRD peak and its position are used to indicate crystallinity, crystal size, And the amount of defects. "Catalytic substances or materials," refers to precursors, chemicals, functional groups, and any other chemical elements capable of catalyzing reactions, particularly hydrocarbon conversion reactions in this art. - S. . 201130739 "Finished form" of a catalyst means a material added directly to a catalytic material or material, and may be of a known form, including particulates, extrudates, monoliths, "alkali metal" Refers to the metal of Group IA, which is a mixture of ionic species of hydroxide (such as NaOH) depending on the possible needs of the invention. The alumina selected for the method of the present invention will be required with the resulting boehmite and boehmite alumina. Varying properties, such as pores, types of catalytic materials or materials combined with alumina, required abrasion resistance. Suitable for treating any embodiment of the invention, not limited to, selected from boehmite, calcined transition phase oxygen , Θ, and η), pseudo-soft boehmite, diaspore, non-calcined aluminum trihydrate, gibbsite, gibbsite, or a mixture of two or more. Rapid calcination of aluminum trihydrate is a particularly suitable alumina, and boehmite is made to be suitable for FCC process. The average particle size of alumina can vary. The average particle size used for the general is Prior to treatment in accordance with the present invention, the alumina may need to include 'milling the alumina into a bead or the like suitable for forming the catalytic reaction described later in the art, or It is the visual quality. For example, the use of alkali kumba stone is the volume of the cavity, the surface area, and the alumina of the finished catalyst, including aluminum, such as ρ, γ crystalline alumina, fast gibbsite, and its stone. The gibbsite, in particular, utilizes the catalyst group used in the present invention within the range of the alumina of the present invention. However, some processing is carried out, and the particle size of the agent particles 201130739 Once the Ming Tuo is selected (and optionally treated as needed), it can be added to the medium for heating. Such a medium is preferably water' and the amount of alumina added to the medium is sufficient to achieve a solids content in the range of 2 to 40% by weight. The alkali metal is also added to the medium', which may be added before, after or simultaneously with the addition of the alumina. Adding a sufficient amount of alkali metal' such that the concentration of the alkali metal (in the form of an alkali metal hydroxide) contained in the medium is at least 〇·2〇 mol/mole bauxite, preferably 0.20 to 2.20, more Good is in the range of 0.2 to 2. Suitable alkali metal hydroxides include sodium, potassium, lithium, and planed hydroxides. Among them, sodium hydroxide or potassium is particularly suitable. The pH of the medium containing alkali metal hydroxide and alumina will depend on the concentration of the alkali metal hydroxide, the type of alkali metal, and the selected alumina. In general, the medium has a pH of 7 or greater and is in the range of 7 to 14. The medium containing the alkali metal hydroxide and alumina is heated to a temperature of at least 1 ° C and the temperature is generally in the range of 100 to 300 ° C. Heating to at least 100 °C can be carried out in the presence of steam and is typically heated to a temperature in the range of 100-300 °C, more preferably in the range of 120 to 250 °C. Heating in the presence of steam is usually carried out in a vacuum vessel. The heating period of the alumina is generally from 1 minute to 48 hours, preferably from 30 minutes to 10 hours. Once the soil has been heated for a certain period of time, it can be recovered from the medium by Boehmite's soil, which is usually recovered by filtration using conventional methods.

-8 - S . 201130739 The boehmite alumina prepared by the present invention can be used to manufacture a catalyst by combining the recovered alumina with a catalytic material or material different from alumina, and then recovering the alumina and the catalytic material or material. The combination is processed into a finished product form. Such alumina is generally processed with other optional ingredients and catalytic materials or materials to produce a finished catalyst. Therefore, the alumina prepared by the present invention can be added as an "active matrix" as a catalyst. The catalytic material or material suitable for use in treating any particular embodiment may be a zeolite which, when used in a hydrocarbon conversion process (e.g., a conventional FCC process), is typically a zeolite. The zeolite may be any zeolite having catalytic activity in a hydrocarbon conversion process. In general, these zeolites may be zeolites having large pores characterized by a pore structure having an opening of at least 7 nanometers, or a mesoporous zeolite characterized by a pore size of less than 0.7 nm but greater than about 0.56. Nano. Suitable large pore zeolites include crystalline aluminosilicate zeolites such as octahedral zeolites, i.e., zeolite Y, zeolite X, and zeolite beta; and their heat treated (calcined) and/or rare earth exchanged derivatives. Particularly suitable zeolites include calcined, rare earth exchanged cerium type zeolite (CREY), the preparation of which is disclosed in U.S. Patent No. 3,042,9,96; ultrastable cerium type (USY), as in U.S. Patent 3,2,93 No. 1,92; and various partially exchanged cerium-type zeolites are disclosed in U.S. Patent Nos. 3,607,043 and 3,676,368. Other suitable large pore zeolites include MgUS®, ZnUS®, MnUS®, Η 、, REY, CREUSY, REUSY zeolites, and mixtures thereof. -9- 201130739 A suitable γ-type zeolite is produced by crystallization of sodium citrate and sodium aluminate. This zeolite can be converted to the USY type by dealumination, which increases the 矽/aluminium atomic ratio of the yttrium zeolite structure. The dealumination can be achieved by steam calcination or by chemical treatment. In a specific embodiment, when the clay microspheres are zeoliated in situ to form a gamma type zeolite, the clay microspheres are formed by calcining the clay microspheres by contacting the caustic solution at 180 °F (82 ec). Y zeolite. Reference may be made to the above-mentioned "Studies in Surface Science and Catalysis". The preferred fresh Y-type zeolite has a unit lattice size of about 24.45 to 24.7A. The unit lattice size (UCS) of the zeolite can be measured by X-ray analysis under the ASTM D3942 specification. The relative amount of bismuth and aluminum atoms in the zeolite is usually proportional to its unit lattice size. This relationship is fully described in DW Breck's Zeolite Molecular Sieves, Structural Chemistry and Use (1 974), page 94, the teachings of which are incorporated by reference. Incorporated herein. Although the zeolite itself and the fluid cracking catalyst matrix typically contain both cerium oxide and aluminum oxide, the SiO2/Al203 ratio of the catalyst matrix should not be confused with the zeolite ratio. When the equilibrium catalyst is subjected to X-ray analysis, only the UC S of the crystalline zeolite contained therein is measured. When the zeolite encounters the environment of the FCC regenerator and reaches equilibrium, the unit lattice size of the zeolite is reduced by the removal of the aluminum atoms from the crystal structure. Therefore, when the zeolite is used in the FCC process, the Si/Al atomic ratio of its structure is increased from about 3:1 to about 3 〇 :]. The unit lattice size will be due to the aluminum atom

-10- S 201130739 The shrinkage caused by the removal of the lattice structure is reduced. Preferably, the equilibrium gamma type zeolite has a unit lattice size of at least 24.2 2 Torr, preferably 24.24 to 24.50 Å, and more preferably 24.28 to 24.44 Å. Suitable medium pore zeolites include pentasil zeolites such as ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-50, ZSM-57, MCM-22, MCM-49, MCM- 56, all of which are known materials. Other zeolites which may be used include zeolites having a metal element other than aluminum (e.g., boron, gallium, iron, chromium). One or more optional additional ingredients in the finished catalyst product include, but are not limited to, a matrix, a binder, and/or a functional additive. As described above, the boehmite alumina of the present invention can be used as an active substrate for the finished catalyst, and other matrix materials such as aluminum obtained by methods other than the present invention can be added to the extent desired. Soil, cerium oxide, porous cerium aluminum oxide, and kaolin. By "active" is meant a material 〇 matrix material that is active in the conversion and/or pyrolysis of hydrocarbons (eg, cracking hydrocarbons in a typical FCC process), ie, the boehmite bauxite of the present invention and any An additional matrix material used in an amount up to about 90% of the total weight of the catalyst composition. The matrix is generally present in an amount ranging from about 20 to about 90% by weight of the catalyst composition, more preferably from about 40 to about 80% by weight. As previously stated, kaolin is a typical substrate which, when used, is The clay component itself constitutes a catalyst composition having a weight of from about 20 to about 60%. » -11- 201130739 Suitable binders include materials capable of binding the matrix and zeolite to the particles. Particularly suitable binders include, but are not limited to, aluminum sol, bismuth sol, alumina (including peptized alumina), and bismuth aluminum oxide. Suitable adhesives also include the alum-derived adhesives disclosed in WO 2008/0〇5155, the disclosure of which is incorporated herein by reference. The above materials are actually precursors for the formation of inorganic oxide binders which are used to bond other components of the viscous composition to the final form having the desired properties, including, but not limited to, during use of the composition. Wear resistance. Accordingly, it is generally desirable to use binders in conjunction with the present invention, and generally employ the present invention to produce particulate catalysts wherein the catalysts have a Davison attrition index in the range of from 1 to 20, preferably from 1 to 15. . It is preferred to add a rare earth to the catalyst composition to enhance the performance of the catalyst in the FCC unit. Suitable rare earths include cerium, lanthanum, cerium, lanthanum, and mixtures thereof, which may be added in the form of a salt to the mixture containing the boehmite alumina of the present invention and the catalytic material or material prior to forming the catalyst. Suitable salts include rare earth nitrates, carbonates, and/or chlorides. The rare earth may also be added to the zeolite via separate exchange with any of the foregoing salts. Other optional additives often used as functional additives in catalytic cracking processes include, but are not limited to, SOx reducing additives, NOx reducing additives, gasoline sulfur reducing additives, C Ο combustion promoters, additives for the manufacture of light olefins. Wait. These additives may be first formed into individually bonded particles' and then combined with boehmite alumina and catalytic materials or materials prior to formation of the catalyst particles. Or, it can be added in the form of salts or other soluble forms.

The active functionality of the -12-S, 201130739 agent (such as vanadium in gasoline sulfur reduction additives) is added to the medium in which the alumina and catalytic material have been combined. It is also possible to mix the separately formed additive particles with the catalyst particles containing the boehmite alumina prepared by the present invention. When manufacturing FCC catalysts, spray drying can be used to treat the boehmite alumina, catalytic materials or materials of the present invention, as well as the components selected to form the finished catalyst. For example, after combining boehmite and zeolite with selected ingredients in water, the resulting slurry is spray dried into granules having an average particle size in the range of from about 20 to about 150 microns, more preferably 40 to 1 μm, and the resulting catalyst particles are then treated under conventional conditions. The catalyst can then be selectively rinsed to remove excess alkali metal, which is known as a catalyst contaminant, especially an FCC catalyst. It is also possible to rinse the boehmite alumina obtained by the present invention before further treating the alumina with a catalytic material or material. In another embodiment, the catalyst and/or boehmite alumina is rinsed one or more times, preferably with an aqueous solution of water and/or ammonium salt (e.g., ammonium sulfate solution). The rinsed catalyst or recovered boehmite is separated from the rinsing slurry by conventional techniques, such as filtration, and dried to reduce the moisture content of the granules to the desired extent, typically at about 100 ° C. It is carried out in a temperature range of up to 300 °C. The spray dried catalyst can be used directly as a finished catalyst or it can be calcined for activation prior to use. For example, the catalyst particles can be calcined at a temperature ranging from about 370 ° C to about 760 ° C for about 20 minutes to about 2

S -1 3- .201130739 hours. The catalyst particles are preferably calcined at a temperature of about 600 ° C for about 45 minutes. The total surface area of any of the foregoing embodiments may range from 100 to 500 square meters per gram, and more typically from 150 to 350 square meters per gram. Thus, a method particularly suitable for use in the manufacture of FCC catalyst particles comprises: (a) selecting boehmite bauxite, gibbsite, flash calcined gibbsite, or mixtures thereof (b) placing the selected bauxite In the medium to be heated, (c) at a temperature of 100 ° C to 300 ° C in the presence of steam and an alkali metal hydroxide concentration in the range of 0.20 to 2.0 m / mol of alumina Heating the selected alumina in range, (d) recovering boehmite from the medium after heating, (e) recovering boehmite and zeolite and selecting from cerium oxide, lanthanum aluminum oxide, clay, Combining one or more components of a group of bauxite different from recycled boehmite and a mixture thereof; and (f) processing a combination of bauxite and a catalytic material or material into a finished catalyst form having an average particle size In the range of 20 to 150 microns. Catalytic processes which can use the catalyst made of the alumina of the present invention, including the FCC method and the hydrotreating treatment method, are known in the art, but are not limited thereto. The catalyst used in the previous method is generally a fine particle having an average particle diameter in the foregoing range, and the latter method is often used as an extrudate having a minimum size of 1 mm or -14 to 201130739. A description of the FCC method can be found in U.S. Patent No. 7,304,011, the disclosure of which is incorporated herein by reference. The following specific examples are presented to further illustrate the invention and its advantages. These examples are intended to be a special description of the invention. However, it is understood that the invention is not limited by the specific details set forth in the examples. Unless otherwise stated, all parts and percentages relating to solids composition or concentration are referred to in the examples and in the remainder of this patent application on a weight basis. In addition, any numerical range recited within the scope of the specification or patent application, such as a particular collection of properties, measurement units, conditions, physical states or percentages, or any number falling within the scope, The subset of numbers so recited herein is specifically recited herein by reference. The following meanings apply to the abbreviations used in the following embodiments. DB = Dry on a dry basis, where the material is dried at 1 75 °F for one hour. C = Celsius temperature Gms or g = g m = REUSY determined by Mo or Mo, Rare earth exchange Ultrastable Y zeolite ppm = 1 part per million wt = weight, "wt%" means weight Percent XRD = X-ray diffraction -15 - 201130739 APS = average particle size ABD = average bulk density DI = Davison attrition index SA = surface area measured by BET Rare earth (eg, lanthanide metal mixture) [Examples] The following is a description of the method for making the present invention and its comparison with other methods. Example 1 (comparative) 714 g of DB boehmite bauxite was slurried in 420,000 g of water. The pH of the slurry was 8.1. The slurry was autoclaved at 188 C for 1 hour. After autoclaving, the slurry was filtered and rinsed with water. The resulting filter cake was adjusted to a slurry containing 29.5% by weight solids in water. A small amount of filter cake was dried in a 120 C laboratory oven for XRD '. The XRD analysis confirmed that the alumina was boehmite. Example 2 'A 714 g DB of boehmite alumina was slurried in 4200 g of water' and then 168 g of 50% NaOH was added to obtain 0.3 m NaOH/mole bauxite. The pH of the slurry was 12.8. The slurry was then autoclaved at 188 C for 1 hour. After autoclaving, the slurry was filtered and rinsed with water. The resulting filter cake was slurried in water to a solid containing 33.7% solids. For XRD, a small amount of filter cake was dried in a 120 C laboratory oven. XRD analysis confirmed that the bauxite was boehmite bauxite. -16- 201130739 Example 3 714 grams of DB boehmite bauxite was conditioned in 4200 grams of water to form a body, and then 2 80 grams of 50% NaOH was added to obtain 0.5 m NaOH / mole alumina. The pH of the slurry was 13.1. The slurry was then autoclaved at 188 C for 1 hour. After autoclaving, the slurry was filtered and rinsed with water. The resulting filter cake was slurried in water containing 30.6% solids. For XRD, a small amount of filter cake was dried in a 120 C laboratory oven. XRD analysis confirmed that the bauxite was boehmite bauxite. Example 4 714 grams of DB boehmite alumina was slurried in 4200 grams of water, and then 392 grams of 50% NaOH was added to obtain 0.7 m NaOH per mole of alumina. The pH of the slurry was 13.1. The slurry was then autoclaved at 188 C for 1 hour. After autoclaving, the slurry was filtered and rinsed with water. The resulting filter cake was slurried in water to a 34% solids. For XRD, a small amount of filter cake was dried in a 120 C laboratory oven. XRD analysis confirmed that the bauxite was boehmite bauxite. Example 5 (comparative) 714 grams of DB AP15 alumina was slurried in 4200 grams of water. AP15 alumina is available from ALCOA. The pH of the slurry was 9.3. The slurry was autoclaved at 188 C for 1 hour. After autoclaving, the slurry is filtered and rinsed with water. The resulting filter cake was slurried in water containing 36.8% solids. For XRD, a small amount of filter cake was dried in a 120 C laboratory oven. XRD analysis confirmed that the alumina was boehmite alumina.

S -17- 201130739 Example 6 714 g of DB AP15 alumina was slurried in water, and then 168 g of 50% NaOH was added to obtain 0.3 m NaOH/mole bauxite. The pH of the slurry was 11.7. The slurry was then autoclaved at 188 C for 1 hour. After autoclaving, the slurry was filtered and rinsed with water. The resulting filter cake was slurried in water containing 30.9 % solids. For XRD, a small amount of filter cake was dried in a 120 C laboratory oven. The XRD analysis confirmed that the alumina was boehmite alumina. Example 7 714 grams of DB AP15 alumina was slurried in water and then 280 grams of 50% NaOH' was added to obtain 0.5 m NaOH / mole alumina. The pH of the slurry was 12.1. The slurry was then autoclaved at 188 C for 1 hour. After autoclaving, the slurry was filtered and rinsed with water. The resulting filter cake was slurried in water to have a solid content of 21.9%. For XRD, a small amount of filter cake was dried in a 120 C laboratory oven. XRD analysis confirmed that the alumina was boehmite alumina. Example 8 714 g of DB API 5 alumina was slurried in water, and then 3 92 g of 50% NaOH was added to obtain 0.7 m NaOH/mole bauxite. The pH of the slurry was 13.2. The slurry was then autoclaved at 188 C for 1 hour. After autoclaving, the slurry is passed through and rinsed with water. The resulting filter cake was slurried in water containing 21.2% solids. For XRD, a small amount of filter cake was dried in a 120 C laboratory oven. The XRD analysis confirmed that the alumina was boehmite alumina.

-18-S 201130739 Example 9 (Control group) The starting gibbsite used in Examples 9-13 was in the form of a water slurry. The slurry contained 37.8% by weight of alumina. 612 g of DB gibbsite (as is 1619 g) was slurried in 3481 g of water. The pH of the slurry was 7.32. The slurry was then autoclaved at 18 5 C for 2 hours. After autoclaving, the slurry is filtered and rinsed with water. The resulting filter cake was slurried in water to contain 24.6% solids. For XRD, a small amount of filter cake was dried in a 120 °C laboratory oven. XRD analysis confirmed that the alumina was boehmite. This preparation and the preparation described in Example 1 〇-1 3 were repeated to multiply the amount of alumina. Example 10 (Example 58 of US 2007/0274903 A1) 612 g of DB gibbsite (as is 1619 g) was slurried in 3470 g of water. The pH of the slurry was 7.32. The pH of the slurry was adjusted to 12 using a 50% NaOH solution. The amount of 50% NaOH used was 9.5 grams. The slurry was autoclaved at 185 C for 2 hours. After autoclaving, the slurry is filtered and rinsed with water. The resulting filter cake was slurried in water containing 22.5 % solids. The NaOH used during the treatment was equal to 0.02 m NaOH/mole bauxite. For XRD, a small amount of filter cake was dried in a 120 C laboratory oven. XRD analysis confirmed that the alumina was boehmite alumina. Example 1 1 612 g of DB gibbsite (as is 1619 g) was slurried in 3337 g of water. The pH of the slurry was 7.32. Add 144 grams of 50% NaOH solution to the slurry. The pH of the slurry was 13.41. The -19-201130739 slurry was autoclaved at 185C for 2 hours. Rinse with water after autoclaving. The resulting filter cake was slurried in water to a slurry solid. The NaOH used during the treatment is equal to | soil. For XRD, a small amount of filter cake was dried at 120 C. XRD analysis confirmed that the alumina was boehmite. Example 1 2 612 g of DB gibbsite (as it was, 16 water was slurried into a slurry. The pH of the slurry was 7.32. gram of 50% NaOH solution. The pH of the slurry was 'pulverized for 2 hours. The water was rinsed after autoclaving. The resulting filter cake was slurried in water to a slurry solid. The NaOH used during the treatment was equal to the soil. For XRD, a small amount was obtained. The filter cake was dried at 120 C. XRD analysis confirmed that the bauxite was boehmite. Example 1 3 612 g of DB gibbsite (as it was a slurry of 16 water. The pH of the slurry was 7.32 " 50% NaOH solution. The pH of the slurry was autoclaved for 2 hours in the slurry. The water was rinsed after autoclaving. The resulting filter cake was slurried in water to a slurry solid. The NaOH used during the treatment was equal to the soil. For XRD, a small amount of filter cake was dried at 120 C. XRD analysis confirmed that the alumina was boehmite, the slurry was filtered and used in a laboratory oven containing 17.5 %).3 m NaOH/moire. Dry alumina. 19 g) Add 240 13.45 to the slurry at 3 24 1 gram. At 185 C, the slurry was filtered and used, which contained 17.2% 0.5 m NaOH/mole in a laboratory oven of dry alumina. • 19 grams) at 3145 grams Add 3 3 6 13.53 to the slurry. At 185 C, the slurry was filtered and used as a dry alumina in a laboratory oven containing 18.9% 0.7 m NaOH/mole aluminum. -20- 201130739 Catalyst Examples 1 - 1 3 Preparation All of the following examples contained 30% RESUY, 15% alumina (from Examples 1-8), 35% clay, and 20% bismuth sol. . For Examples 1-8, the RESUY slurry had a solids content of 32%. For Examples 9-13, the RESUY slurry had a solids content of 38.2%. The clay contains 85% solids. The cerium sol contains 10% solids. The slurry containing RESUY and alumina was honed, and after honing, the pH was adjusted to 3.8 using 20% H2S04. The cerium sol and the clay are added to the slurry, and the entire slurry is well stirred. The slurry is then spray dried. The spray dried catalyst was first slurried with NH4OH at a pH of 7-9., followed by exchange with (nh4) 2so4 solution. Finally, the catalyst is placed in an oven for drying. Catalyst Example 1 Using 3177 grams of RESUY slurry, 1723 grams of the alumina slurry of Example 1, 6778 grams of cerium sol, and 1395 grams of clay to make the catalyst catalyst Example 2 Using 3254 grams of RESUY slurry, 1544 g of the alumina slurry of Example 2, 6942 g of cerium sol, and 1 429 g of clay were used to make the catalyst-2 1-201130739 catalyst to make the slurry, the ruthenium catalyst to make the slurry, the ruthenium catalyst to make the slurry, The ruthenium catalyst allowed the slurry, the ruthenium catalyst to make the slurry, the 0 catalyst to make the slurry, the Example 3 to use 3 025 g of RESUY slurry, the 6454 g of ruthenium sol, and the 1329 Example 4 with 2922 g of RESUY slurry, 623 4 grams of cerium sol, and 1283 Example 5 were treated with 3218 grams of RESUY slurry, 6866 grams of cerium sol, and 1414 Example 6 with 2889 grams of RESUY slurry, 63 74 grams of cerium sol, and 1312 Example 7 Using 3 04 8 grams of RESUY slurry, 6502 grams of cerium sol, and 1339 Example 8 using 3107 grams of RESUY slurry, 6628 grams of cerium sol, and 1364 1581 grams of the aluminous clay of Example 3. To make 1375 grams of the clay of the aluminum gram of Example 4 to make the catalyst 1399 g of the aluminous gram clay of Example 5 was prepared to make 1547 g of the aluminous gram clay of Example 6 to prepare a catalyst 2226 g of the aluminous gram clay of Example 7 to prepare a catalyst of 2345 g. Example 8 Alumina gram clay to make a catalyst•22-.201130739 Catalyst Example 9 3168 grams of RESUY slurry, 2460 grams of the alumina slurry of Example 9, 8068 grams of cerium sol, and 1661 grams were used. Clay to Make Catalyst Rhodium Catalyst Example 1 A catalyst was prepared using 3542 grams of RESUY slurry, 3007 grams of the alumina slurry of Example 10, 9020 grams of cerium sol, and 1 857 grams of clay. Catalyst Example 1 1 A catalyst was prepared using 3455 grams of RESUY slurry, 3771 grams of the alumina slurry of Example 11, 8800 grams of cerium sol, and 1812 grams of clay. Catalyst Example 1 2 A catalytic agent was prepared using 3 375 g of RESUY slurry '3748 g of the alumina slurry of Example 12, 8596 g of cerium sol, and 1770 g of clay. Catalyst Example 1 3 A catalyst was prepared using 3429 grams of RESUY slurry, 3465 grams of the alumina slurry of Example 13, 8732 grams of cerium sol, and 1798 grams of clay. Deactivation of Catalyst Examples 1-3 3 Each catalyst example was deactivated in the presence of 1000 ppm Ni + 2000 ppm V using a -23-g 201130739 CPS specification well known in the art. See Lori T. Boock, Thomas F. Petti, and John A. Rudesill, / CS·琢款会# The Department of Literature, 04, 1996, pp. 171-183. The properties of the catalysts of Catalyst Examples 1-3 before and after deactivation are described in Tables 1-3 below. Table 1 Example 1 Example 2 Example 3 Example 4 ai2o3, heavy view % 33.7 34.4 34.3 34.6 Na2. , 重景% 0.2 0.22 0.23 0.22 SO#, wt% 0.51 0.4 0.41 0.39 Re203, heavy view % 1.67 1.87 1.87 1.89 APS, micron 62 58 59 58 ABD, g / cm ^ 3 0.79 0.78 0.79 0.8 DI 1 2 3 2 Lattice Size, A 24.6 24.6 24.6 24.6 Zeolite SA, m ^ 2 / g 162 180 179 184 Substrate SA, m ^ 2 / g 75 69 73 74 3000 ppm Ni + VCPS Ni ppm 1111 1157 1104 1211 V ppm 2240 2200 2220 2350 Lattice Size, A 24.26 24.26 24.26 24.26 Zeolite SA, m ^ 2 / g S6 105 102 107 Substrate SA, m ^ 2 / g 39 31 31 31 Table 2 Example 5 Example 6 Example 7 Example 8 Al2〇3, Ray Amount % 31.4 32.2 32.4 32 NazO, heavy view % 0.2 0.21 0.23 0.29 SO#, Thunder% 0.58 0.46 0.62 0.42 Re203, Re-view % 1.53 1.6 1.6 1.64 APS, micron 62 67 63 67 ABD, g/cm ^ 3 0.84 0.82 0.79 0.72 DI 1 1 3 2 lattice size, a 24.6 24.61 24.6 24.61 Zeolite SA, m ^ 2 152 157 167 193 Substrate SA, m ^ 2 to 60 67 61 46 3000 ppm Ni + VCPS Ni ppm 1057 1104 1129 1159 V ppm 1990 2220 2200 2260 lattice size, A 24.26 24.25 24,26 24.26 Zeolite SA, square meters 80 83 93 88 Matrix SA, square meters 22 27 21 17 -24- 201130739 Table 3 Example 9 Example 10 Example 11 Example 12 Example 13 A1203, Weight % 35.7 35.8 35.3 35.1 34.8 Na20, Thunder% 0.27 0.24 0.27 0.28 〇S〇4, wt% 1.03 0.88 0.69 0.61 0 54 Re2〇3, Thunder% 1.86 1.77 1.77 1.75 1 73 APS, micron 59 54 53 54 54 ABD, square 颂 0.79 0.79 0.78 0.76 0.75 DI 2 0 1 4 〇 lattice size, A 24.61 24.61 24.61 24.61 24 61 琢石SA, square meters 浣 151 156 153 151 153 matrix SA, square meters now 33 32 44 45 54 3000 ppm Ni + VCPS Ni ppm 983 1031 1156 1023 1043 V ppm 2110 2010 2060 2020 2030 Lattice size, A 24.26 24.26 24.27 24.26 J 24.27 Zeolite SA, square meters 73 77 89 83 94 Matrix SA, m ^ 2 /克 16 12 12 18 17 ACE performance evaluation after deactivation A deactivation sample was evaluated in an ACE model AP fluidized bed microreactive unit made by Kayser Technologies. Also refer to US 6, 〇69012. The temperature of the reactor was 538 °C. The raw materials used in the evaluation have the following properties. Properties of Raw Materials for ACE Testing API Gravity @60°F 20.6 Conradson Residual Carbon, Childhood % 5.1 K Factor 11.76 Refractive Index 1.522236 API Meaning can be found in Compositions and Analysis of Heavy Petroleum Fractions , Marcel Dekker (1990), page 107. In short, it is defined as API = (141.5 / [the specific gravity of the feed at 60 °F]) _ 131.5.

Conradson residual carbon refers to the coking tendency of the raw materials. See Composition and Analysis of Heavy Oil Fractionation, Marcel Dekker (1990), p. 145, and ASTM D189. -25- 201130739 The K factor is a composite parameter for raw materials used to estimate the paraffin content of crude oil. This parameter is based on the average boiling point and specific gravity of the feedstock. See the composition and analysis of heavy oil fractionation, Marcel Dekker (1 990), page 15 on page 15 for notes. The results of the ACE test are illustrated in Figures 1-9 of the accompanying drawings, which show catalysts containing the boehmite alumina prepared in accordance with the present invention and catalysts prepared from other aluminas (including US Patent 2007/0274903). Compared to the catalyst prepared with the pH adjuster described above, it has excellent catalyst performance, and the result is lower coke, less hydrogen for some specific examples, and higher Gasoline production. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view for explaining the amount of coke deposited during the simulated FCC method (ACE) using a catalyst containing alumina (hereinafter, Examples 2-4) produced by various embodiments of the present invention ( % by weight) relative to the hydrocarbon conversion (% by weight) during the FCC process. The alumina of the present invention is prepared from boehmite alumina, and the catalyst prepared therefrom is compared with the catalyst prepared by the prior art alumina (Example 1 below). ACE refers to the laboratory-scale catalyst test methodology as described in the following examples. Figure 2 is a diagram for explaining the amount (% by weight) of hydrogen produced during the simulated FCC process (ACE) using a catalyst comprising alumina (hereinafter referred to as Example 2·4) produced by various embodiments of the present invention relative to FCC The relationship between hydrocarbon conversion (% by weight) during the process. This is a comparison of the catalyst prepared by the production of alumina of the present invention with the catalyst prepared by the alumina produced by the conventional method (Example 1 below). -26- 201130739 Fig. 3 is a diagram for explaining the use of a catalyst containing the alumina produced by various embodiments of the present invention (Examples 2-4 below) by a simulated FCC method (ACE) (C5 and heavier) Olefin fraction> The relationship between the amount of the product (% by weight) relative to the hydrocarbon conversion rate (% by weight) during the FCC process, which is the alumina produced by the method of the present invention and the alumina produced by the old method (hereinafter Example 1) The prepared catalysts were compared. Figure 4 is intended to illustrate the use of a catalyst comprising alumina (see Examples 6-8 below) prepared in accordance with various embodiments of the present invention during the simulated FCC process (ACE). The amount of coke deposited (% by weight) relative to the hydrocarbon conversion (% by weight) during the FCC process. The alumina of the present invention is prepared from gamma alumina or rapidly calcined gibbsite and prepared therefrom. The catalyst was compared with a catalyst prepared from an alumina (the following Example 5) produced by the conventional method. Fig. 5 is a view for explaining the use of alumina prepared by various embodiments of the present invention (Example 6 below) 8) The catalyst is in The amount of hydrogen (% by weight) produced during the FCC process (ACE) relative to the hydrocarbon conversion (% by weight) during the FCC process. The alumina of the present invention is prepared from gamma alumina or rapidly calcined gibbsite. And the catalyst prepared by the same is compared with the catalyst prepared by the prior art alumina (Example 5 below). Fig. 6 is for explaining the use of alumina produced by various embodiments of the present invention. (Examples 6-8 below) Catalysts The amount of gasoline (C5 and heavier olefin fractions) obtained by the simulated FCC process (ACE) (% by weight) relative to the hydrocarbon conversion (% by weight) during the FCC process Relationship. The invention

S -27- 201130739 Alumina is prepared from rapidly calcined gibbsite and the catalyst prepared therefrom is compared with the catalyst prepared by the prior art alumina (Example 5 below). Figure 7 is a diagram for explaining the amount (% by weight) of coke deposited during the simulated FCC process (ACE) using a catalyst comprising alumina (hereinafter referred to as Example H-13) produced by various embodiments of the present invention relative to FCC The relationship between hydrocarbon conversion (% by weight) during the process. The aluminous earth of the present invention is prepared by rapidly calcining gibbsite, and the catalyst prepared therefrom is compared with a catalyst prepared according to the gibbsite produced in U.S. Patent Application No. 2007/0274903 (Example 10 below). . The catalyst prepared from the alumina of the present invention (Examples 11-13) was also compared with the catalyst of the other comparative alumina described in Example 9. Figure 8 is a diagram for explaining the amount (% by weight) of hydrogen produced during the simulated FCC process (ACE) using a catalyst comprising alumina (Example H-1 3) produced by various embodiments of the present invention relative to the FCC method. Relationship between hydrocarbon conversion rate (% by weight) during the period. The invention is prepared by rapid calcination of samarite and the catalyst prepared therefrom is compared to a catalyst prepared according to the gibbsite (Example 10) produced in accordance with U.S. Patent Application Serial No. 2007/0274903. The catalyst prepared from the alumina of the present invention (Example 1 1 · 13) was also compared with the catalyst of another comparative alumina described in Example 9. Figure 9 is a diagram for illustrating the amount of gasoline (C 5 and heavier olefin fraction) products obtained by the simulated FCC process (ACE) using a catalyst comprising alumina (Examples 11-13) produced by various embodiments of the present invention. (% by weight) relative to the hydrocarbon conversion (% by weight) during the FCC process of -28-201130739. This was prepared by rapid calcination of gibbsite, and the catalysts prepared in accordance with U.S. Patent Application No. 2007/0274903, which is incorporated herein by reference. The catalyst prepared from the aluminum 1 1 -1 3) of the present invention was also compared with the catalyst prepared in the same manner as in Example 9. [Main component symbol description] None. I Ming Alumina I agent and yttrium (implemented soil (example - comparison of aluminum -29-

Claims (1)

201130739 VII. Patent application scope: 1. A method for manufacturing boehmite bauxite 'This method includes: a. Selecting bauxite' b. Placing bauxite in a medium to heat it' c. Alkali metal hydroxide The selected alumina is heated at a temperature of 100 ° C or higher at a concentration of at least 〇 2 mol / moor soil, and d. After heating, the boehmite alumina is recovered from the medium. . 2. The method of claim 1, wherein the alumina in (a) is selected from the group consisting of boehmite, calcined transition phase alumina, pseudo-soft boehmite, gibbsite, diaspore, One of a group consisting of rapidly calcined aluminum trihydrate, gibbsite, amorphous alumina, nodilite, and a mixture of two or more thereof. 3_ The method of claim 1, wherein the heating in (c) is in the range of 100 to 300 °C. 4. The method of claim 3, wherein the heating is carried out in the presence of steam. 5. The method of claim 1, wherein the alkali metal hydroxide is selected from the group consisting of sodium, potassium, lithium, planer, and mixtures thereof. 6. The method of claim 1, wherein the alkali metal of the alkali metal hydroxide comprises sodium 'potassium or a mixture thereof. -30- 201130739 7. If the method of claim 1 is applied, a further package is included. (e) The alkali metal is removed from the recovered boehmite bauxite. 8. The method of claim 1, wherein the alkali metal hydroxide concentration is in the range of from 0.2 to 2.20 moles per mole of alumina. 9. A method of making a catalyst, the method comprising: a. selecting alumina, b. placing the alumina in a medium that heats it, c. at an alkali metal hydroxide concentration of at least 0.2 moles per mole of aluminum Under the condition of soil, the selected bauxite is heated at a temperature of 100 ° C or higher. d. After heating, the boehmite bauxite is recovered from the medium, e. The recovered boehmite bauxite is different from the recovery a catalytic material or material combination of boehmite bauxite, and f. processing a combination of bauxite and catalytic material or material into a finished catalyst form. 10. The method of claim 9, wherein the method further comprises removing alkali metal from the recovered boehmite bauxite. 11. The method of claim 10, wherein the removing the alkali metal from the recovered boehmite alumina is performed by rinsing prior to combining it with the catalytic material or material. 12. The method of claim 1, wherein the method comprises: removing the alkali metal from the recovered boehmite bauxite after processing the combination of the alumina and the catalytic material or material into a finished catalyst form. 1-201130739. The method of claim 9, wherein one or more additional components are combined with the recovered alumina and catalytic material or material in step (d), the additional component comprising a matrix, a binder, and One of the groups of additives. The method of claim 13, wherein the one or more additional components comprise an ingredient selected from the group consisting of clay, strontium aluminum oxide, cerium oxide, and mixtures thereof. 15. The method of claim 9, wherein the catalyst material or material comprises zeolite. 16. The method of claim 15, wherein the zeolite is selected from the group consisting of USY, REUSY, faujasite, ZSM5, and mixtures thereof. 17. The method of claim 9, wherein the alumina in (a) is selected from the group consisting of boehmite, calcined transition phase alumina, pseudo-soft boehmite, diaspore, and rapid calcination of aluminum trihydrate. a group of gibbsite, amorphous alumina, gibbsite, nodilite, and a mixture of two or more thereof. 18. The method of claim 9, wherein the heating in (c) is in the range of 100 to 300 °C. The method of claim 18, wherein the heating is carried out in the presence of steam. 20. The method of claim 9, wherein the alkali metal hydroxide is selected from the group consisting of A group of sodium, potassium, lithium, planers, and mixtures thereof. 5 - 32 - • 201130739 21. The method of claim 9, wherein the alkali metal of the alkali metal hydroxide comprises sodium, potassium and a mixture thereof. 22. The method of claim 9, wherein the alkali metal hydroxide concentration is in the range of 0.20 to 2.20 moles per mole of alumina. 23. The method of claim 9, wherein the alumina in (a) is selected from the group consisting of boehmite, gibbsite, rapidly calcined gibbsite, and mixtures thereof; The heating in c) is carried out in the range of 100 to 300 ° C under the condition that steam is present and the alkali metal hydroxide concentration is in the range of 0.20 to 2.0; the catalyst substance in (e) contains zeolite And one or more additional components are combined with the recovered alumina and zeolite, wherein one or more additional components are selected from the group consisting of cerium oxide, cerium aluminum oxide, clay, alumina different from recycled alumina, and mixtures thereof. Groups; and selected combinations of alumina, zeolite, and one or more additional ingredients are processed in (f) into particles having an average particle size in the range of 20 to 100 microns. 24. The method of claim 23, wherein the alkali metal is removed from the boehmite alumina by rinsing prior to its combination with the catalytic material or material or by moving the alkali metal from the particles via rinsing particles except. -33-