US4081406A — Preparation of catalysts of predetermined pore si…

Claim 1

Independent Claim 329 words

In a process for the formation of a catalyst comprised of a Group VI-B or Group VIII metal, or both, composited with alumina in a series of steps which include precipitating alumina hydrogel from a solution which contains a hydrous form of alumina in concentration ranging from about 1 to about 5 percent, based on the weight of the solution, and a compound having an anion which forms an alkaline soluble aluminum salt in an alkaline medium, at temperatures ranging from about 15° F. to about 120° F. and pH ranging from about 8 to about 12, separating said alumina hydrogel from said alkaline solution, contacting said alumina hydrogel with a solution of a water soluble polymer containing from about 2 to about 24 monomer units from the group consisting of (a) polyethylene glycols, (b) polypropylene glycols, and (c) polyethylene amines sufficient to absorb the polymer into the pores of the alumina hydrogel and displace water from the pores until the weight ratio of polymer: alumina within the hydrogel ranges from about 0.5:1 to about 4:1, forming a slurry of the polymer containing alumina hydrogel, spray drying said slurry of polymer containing alumina hydrogel by countercurrent contact of an atomized spray of the alumina hydrogel with air at temperature sufficient to form granules of boehmite, forming a paste from the granules of polymer containing boehmite and water, the paste containing at least about 20 percent by weight of solids, and mulling said water soluble polymer containing boehmite paste to provide a substantially homogeneous mass, the improvement comprising: extruding said polymer containing boehmite paste through a die to form spaghetti-like extrudate shapes by applying a torque ranging from about 25 to about 55 inch pounds, sizing and shaping the boehmite, contacting and extracting said boehmite shapes with a solvent to separate and remove the water soluble polymer therefrom, and then drying and calcining the shapes, and converting the boehmite shapes from which the polymer has been extracted to gamma alumina.

Claim 2

Dependent Claim 329 words

In a process for the formation of a catalyst comprised of a Group VI-B or Group VIII metal, or both, composited with alumina in a series of steps which include precipitating alumina hydrogel from a solution which contains a hydrous form of alumina in concentration ranging from about 1 to about 5 percent, based on the weight of the solution, and a compound having an anion which forms an alkaline soluble aluminum salt in an alkaline medium, at temperatures ranging from about 15° F. to about 120° F. and pH ranging from about 8 to about 12, separating said alumina hydrogel from said alkaline solution, contacting said alumina hydrogel with a solution of a water soluble polymer containing from about 2 to about 24 monomer units from the group consisting of (a) polyethylene glycols, (b) polypropylene glycols, and (c) polyethylene amines sufficient to absorb the polymer into the pores of the alumina hydrogel and displace water from the pores until the weight ratio of polymer: alumina within the hydrogel ranges from about 0.5:1 to about 4:1, forming a slurry of the polymer containing alumina hydrogel, spray drying said slurry of polymer containing alumina hydrogel by countercurrent contact of an atomized spray of the alumina hydrogel with air at temperature sufficient to form granules of boehmite, forming a paste from the granules of polymer containing boehmite and water, the paste containing at least about 20 percent by weight of solids, and mulling said water soluble polymer containing boehmite paste to provide a substantially homogeneous mass, the improvement comprising: extruding said polymer containing boehmite paste through a die to form spaghetti-like extrudate shapes by applying a torque ranging from about 25 to about 55 inch pounds, sizing and shaping the boehmite, contacting and extracting said boehmite shapes with a solvent to separate and remove the water soluble polymer therefrom, and then drying and calcining the shapes, and converting the boehmite shapes from which the polymer has been extracted to gamma alumina.

Claim 3

Dependent Claim 44 words

The process of claim 1 wherein the Group VIB or Group VIII metal, or both, is composited with the alumina by impregnation of the alumina hydrogel with a solvent containing a compound, or compounds, of the Group VIB or Group VIII metal, or both.

Claim 4

Dependent Claim 24 words

The process of claim 1 wherein the Group VIB or Group VIII metal, or both, is composited with the dried, calcined gamma alumina shapes.

Claim 5

Dependent Claim 97 words

The process of claim 1 wherein, (a) when the catalyst ranges from about 1/50 inch up to about 1/25 inch particle size diameter, it is characterized as follows: ______________________________________ Surface Area, m.sup.2 /g 200-500 Pore Volume, cc/g 0.5-1.5 Pore Size Distributions, cc/g 100-200A >0.3 200-400A >0.05 400A+ <0.2 1000A+ <0.1 ______________________________________ and (b) when the catalyst ranges from about 1/25 inch up to about 1/8 inch particle size diameter, it is characterized as follows: ______________________________________ Surface Area, m.sup.2 2/g 200-500 Pore Volume, cc/g 0.7-1.7 Pore Size Distributions, cc/g 100-200A >0.3 200-400A >0.05 400A+ <0.2 100A+ <0.1 ______________________________________

Claim 6

Dependent Claim 97 words

The process of claim 1 wherein, (a) when the catalyst ranges from about 1/50 inch up to about 1/25 inch particle size diameter, it is characterized as follows: ______________________________________ Surface Area, m.sup.2 /g 225-325 Pore Volume, cc/g 0.7-1.1 Pore Size Distributions, cc/g 100-200A >0.4 200-400A >0.1 400A+ <0.1 100A+ <0.05 ______________________________________ and (b) when the catalyst ranges from about 1/25 inch up to about 1/8 inch particle size diameter, it is characterized as follows: ______________________________________ Surface Area, m.sup.2 /g 250-350 Pore Volume, cc/g 0.8-1.3 Pore Size Distributions, cc/g 100-200A >0.4 200-400A >0.01 400A+ <0.1 1000A+ <0.05 ______________________________________

Claim 7

Dependent Claim 25 words

The process of claim 1 wherein the extrudate shapes are contacted with solvent to extract the polymer, then dried and calcined to form gamma alumina.

Claim 8

Dependent Claim 24 words

The process of claim 6 wherein the Group VIB or VIII metal, or both, is composited with the dried, calcined, gamma alumina extrudate shape.

Claim 9

Dependent Claim 97 words

The process of claim 7 wherein (a) when the catalyst ranges from about 1/50 inch up to about 1/25 inch particle size diameter, it is characterized as follows: ______________________________________ Surface Area, m.sup.2 /g 200-500 Pore Volume, cc/g 0.5-1.5 Pore Size Distributions, cc/g 100-200A >0.3 200-400A >0.05 400A+ <0.2 1000A+ <0.1 ______________________________________ and (b) when the catalyst ranges from about 1/25 inch up to about 1/8 inch particle size diameter, it is characterized as follows: ______________________________________ Surface Area, m.sup.2 /g 200-500 Pore Volume, cc/g 0.7-1.7 Pore Size Distributions, cc/g 100-200A >0.3 200-400A >0.05 400A+ <0.2 1000A+ <0.1 ______________________________________

Claim 10

Dependent Claim 97 words

The process of claim 7 wherein (a) when the catalyst ranges from about 1/50 inch up to about 1/25 inch particle size diameter, it is characterized as follows: ______________________________________ Surface Area, m.sup.2 /g 225-325 Pore Volume, cc/g 0.7-1.1 Pore Size Distributions, cc/g 100-200A >0.4 200-400A >0.1 400A+ <0.1 1000A+ <0.05 ______________________________________ and (b) when the catalyst ranges from about 1/25 inch up to about 1/8 inch particle size diameter, it is characterized as follows: ______________________________________ Surface Area, m.sup.2 /g 250-350 Pore Volume, cc/g 0.8-1.3 Pore Size Distributions, cc/g 100-200A >0.4 200-400A >0.1 400A+ <0.1 1000A+ <0.05 ______________________________________

Claim 11

Dependent Claim 122 words

The process of claim 1 wherein the spaghetti-like extrudate shapes are dried, marumerized to form spheres, contacted with solvent to extract the polymer, dried and calcined to form gamma alumina spheres, which (a) when the spheres range from about 1/50 inch up to about 1/25 inch particle size diameter, are characterized as follows: ______________________________________ Surface Area, m.sup.2 /g 200-500 Pore Volume, cc/g 0.5-1.5 Pore Size Distributions, cc/g 100-200A >0.3 200-400A >0.05 400A+ <0.2 1000A+ <0.1 ______________________________________ and (b) when the spheres range from about 1/25 inch up to about 1/8 inch particle size diameter, they are characterized as follows: ______________________________________ Surface Area, m.sup.2 /g 200-500 Pore Volume, cc/g 0.7-1.7 Pore Size Distributions, cc/g 100-200A >0.3 200-400A >0.05 400A+ <0.2 1000A+ <0.1 ______________________________________

Claim 12

Dependent Claim 96 words

The process of claim 10 wherein (a) when the spheres range from about 1/50 inch up to about 1/25 inch particle size diameter, they are characterized as follows: ______________________________________ Surface Area, m.sup.2 /g 225-325 Pore Volume, cc/g 0.7-1.1 Pore Size Distributions, cc/g 100-200A >0.4 200-400A >0.1 400A+ <0.1 1000A+ <0.05 ______________________________________ and (b) when the spheres range from about 1/25 inch up to about 1/8 inch particle size diameter, are characterized as follows: ______________________________________ Surface Area, m.sup.2 /g 250-350 Pore Volume, cc/g 0.8-1.3 Pore Size Distributions, cc/g 100-200A >0.4 200-400A >0.1 400A+ <0.1 1000A+ <0.05 ______________________________________

Claim 13

Dependent Claim 23 words

The process of claim 10 wherein the Group VIB or VIII metal, or both, is composited with the dried, calcined gamma alumina spheres.

Claim 14

Dependent Claim 55 words

The process of claim 1 wherein the alumina hydrogel is precipitated by combining solutions (a) a first of which contains an alkali metal aluminate and (b) a second of which contains a strong mineral acid or an aluminum salt of a strong mineral acid, the anion portion of which is soluble in the alkaline solution.

Claim 15

Dependent Claim 12 words

The process of claim 1 wherein silica is added to the solution.

Claim 16

Dependent Claim 19 words

The process of claim 1 wherein the temperature of precipitation ranges from about 32° F to about 70° F.

Claim 17

Dependent Claim 29 words

The process of claim 1 wherein the concentration of alumina contained within the solution ranges from about 2 to about 3 percent, based on the weight of the solution.

Claim 18

Dependent Claim 18 words

The process of claim 1 wherein the pH of the solution ranges from about 9 to about 10.

Claim 19

Dependent Claim 15 words

The process of claim 1 wherein the precipitated alumina hydrogel is washed at ambient temperature.

Claim 20

Dependent Claim 21 words

The process of claim 1 wherein the hydrogel is washed at temperatures ranging from about 70° F to about 85° F.

Claim 21

Dependent Claim 23 words

The process of claim 1 wherein the water soluble polymer contains from about 4 to about 8 monomer units in the total molecule.

Claim 22

Dependent Claim 33 words

The process of claim 1 wherein the polymer displaces water from the pores of the alumina hydrogel until the weight ratio of polymer:alumina within the hydrogel ranges from about 1:1 to about 2:1.

Claim 23

Dependent Claim 42 words

The process of claim 1 wherein the polymer containing alumina hydrogel is spray dried at air temperatures ranging from about 250° to about 350° F to form the boehmite, the temperature of the boehmite per se being maintained below about 250° F.

Claim 24

Dependent Claim 25 words

The process of claim 22 wherein the polymer containing alumina hydrogel is spray dried at air temperatures ranging from about 275° to about 300° F.

Claim 25

Dependent Claim 27 words

The process of claim 22 wherein the boehmite is formed as a granulated solid of average particle size diameter ranging from about 75 to about 125 microns.

Claim 26

Dependent Claim 29 words

The process of claim 22 wherein, after the spray drying step, granulated boehmite is formed, and water is added back to the boehmite to form an extrudable homogeneous paste.

Claim 27

Dependent Claim 20 words

The process of claim 25 wherein the extrudable homogeneous paste contains from about 26 to about 32 weight percent alumina.

Claim 28

Dependent Claim 94 words

The process of claim 25 wherein the granulated boehmite paste is extruded by applying a torque ranging from about 40 inch-pounds to about 50 inch-pounds, the solids content of the extrudable homogeneous paste is controlled, and the relationship between the solids content of the paste, extrudate diameter and the average spherical size diameter of the spherical particles to be ultimately formed from extrudates are as follows: ______________________________________ Solids Content Extrudate Average Sphere of the Paste, Diameter, Size Diameter, Wt. % Inches Inches ______________________________________ 30-32 1/55-1/28 1/50-1/25 28-30 1/32-1/21 1/25-[1/6] 1/16 26-28 1/24-1/12 1/16-1/8 ______________________________________

Claim 29

Dependent Claim 31 words

The process of claim 27 wherein the spheres are dried, calcined to form gamma alumina and the Group VIB or VIII metal, or both, is composited with the gamma alumina spheres.

Claim 30

Dependent Claim 96 words

The process of claim 28 wherein (a) when the spheres range from about 1/50 inch up to about 1/25 inch particle size diameter, they are characterized as follows: ______________________________________ Surface Area, m.sup.2 /g 200-500 Pore Volume, cc/g 0.5-1.5 Pore Size Distributions, cc/g 100-200A >0.3 200-400A >0.05 400A+ <0.2 1000A+ <0.1 ______________________________________ and (b) when the spheres range from about 1/25 inch up to about 1/8 inch particle size diameter, are characterized as follows: ______________________________________ Surface Area, m.sup.2 /g 200-500 Pore Volume, cc/g 0.7-1.7 Pore Size Distributions, cc/g 100-200A >0.3 200-400A >0.05 400A+ <0.2 1000A+ <0.1 ______________________________________

Claim 31

Dependent Claim 96 words

The process of claim 28 wherein (a) when the spheres range from about 1/50 inch up to about 1/25 inch particle size diameter, they are characterized as follows: ______________________________________ Surface Area, m.sup.2 /g 225-325 Pore Volume, cc/g 0.7-1.1 Pore Size Distributions, cc/g 100-200A >0.4 200-400A >0.1 400A+ <0.1 1000A+ <0.05 ______________________________________ and (b) when the spheres range from about 1/25 inch up to about 1/8 inch particle size diameter, are characterized as follows: ______________________________________ Surface Area, m.sup.2 /g 250-350 Pore Volume, cc/g 0.8-1.3 Pore Size Distributions, cc/g 100-200A >0.4 200-400A >0.1 400A+ <0.1 1000A+ <0.05 ______________________________________

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1981-03-27	1981-09-26	1982-03-28	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1985-03-27	1985-09-26	1986-03-28	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1989-03-27	1989-09-26	1990-03-28	$7700.00	Window Closed / Lapsed

Preparation of catalysts of predetermined pore size distribution and pore volume

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