# US 5,348,924 A · Zeolite aggregates and catalysts > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,348,924 A - Document ID: US5348924A - Status: Granted - Kind: A - Application number: 08/023,733 - Filed: 1993-02-23 - Granted: 1994-09-20 - Earliest claimed: 1989-09-29 - Assignees: Exxon Research & Engineering Co. - Inventors: Mark J. Potter; Jar-Lin Kao; Virginia R. Cross; Thomas H. Vanderspurt; Edward K. Dienes; Robert E. Riley; Freddie L. Tungate; Arie Bortinger - Web page: https://patentgrep.com/patent/US5348924A ## CPC - B01J 37/0009: {Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst} - B01J 20/186: {Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity} - B01J 29/60: of the type L, as exemplified by patent document US3216789 - B01J 29/62: Noble metals - B01J 29/90: Regeneration or reactivation - C10G 35/095: containing crystalline alumino-silicates, e.g. molecular sieves {(C10G35/065 takes precedence)} - B01J 2229/36: Steaming - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES ## Abstract A process for producing zeolite aggregates involves providing a formable paste composed of zeolite, a binder composed of an organic/metal oxide containing aluminum, a peptizing agent and water; forming the paste into an aggregate, preferably by extruding into an extrudate; curing the aggregate; hydro-thermally calcining the aggregate; and washing the hydro-thermally calcined aggregate with a washing medium, preferably followed by rinsing with a rinsing medium to remove residual washing medium from the aggregate. The washed and rinsed aggregate may then be permitted to equilibrate or is subjected to a drying procedure. Preferably, the washed and rinsed aggregate is again subjected to curing/hydro-thermal calcining. The resultant aggregates, such as extrudates, have an exterior surface with openings and interstitial spaces between particles of binder and zeolite which communicate by such openings between the exterior surface of the aggregate and micropores of the zeolite; the aggregates also exhibit characteristics of crush strength greater than about 0.9 pounds per millimeter and a loss by attrition of less than about 3.0%. Regenerable catalysts, such as reforming catalysts, based on such aggregate also exhibit a catalyst activity pass through to the zeolite bound in the aggregate of at least 70% of the initial catalyst activity of freshly prepared zeolite, as well as exhibiting more than about 70% of the reforming benzene yield that the reforming catalyst exhibited when similarly tested prior to being exposed to a hydrocarbon stream under specified reforming conditions of the catalyst activity test procedures. ## Claims ### Claim 1 A process for producing hardened zeolite aggregates from aggregates made from a formable paste comprising zeolite, an inorganic oxide containing aluminum, a peptizing agent and water, said process comprising the following steps in sequence: a) curing said aggregate under a humid atmosphere at a temperature between about 180.degree. F. and about 250.degree. F. to induce initial hardening phase transitions in said aggregate to result in a cured aggregate; b) hydro-thermally calcining said cured aggregate under a humid atmosphere at temperatures between about 400.degree. F. and about 1400.degree. F. for a time to complete the hardening phase transitions to result in a hydro-thermally calcined aggregate; and c) washing said hydro-thermally calcined aggregate with an aqueous solution of base to remove detritus and neutralize acidity followed by rinsing said washed aggregate with water. ### Claim 2 (depends on 1) The process in accordance with claim 1, wherein said curing at said temperatures is performed for a time within a range of about 1 to about 20 hours. ### Claim 3 (depends on 2) The process in accordance with claim 2, wherein said curing comprises subjecting said aggregate to a temperature of about 195.degree. F. ### Claim 4 (depends on 3) The process in accordance with claim 3, wherein said curing at said temperatures is performed for a time within the range of about 2 to 6 hours. ### Claim 5 (depends on 1) The process in accordance with claim 1, wherein said humid atmosphere comprises a volume percent water within the range of about 40% to about 100%. ### Claim 6 (depends on 1) The process in accordance with claim 1, wherein said time is less than about 15 hours. ### Claim 7 (depends on 1) The process in accordance with claim 1, wherein said hydro-thermal calcining comprises raising the temperature of said aggregate from an initial temperature to a first target temperature within a range of about 400.degree. F. to about 700.degree. F. ### Claim 8 (depends on 7) The process in accordance with claim 7, wherein said first target temperature is about 570.degree. F. ### Claim 9 (depends on 7) The process in accordance with claim 7, wherein said raising the temperature of said aggregate comprises increasing the temperature of said aggregate from an initial temperature to said target temperature at a rate within the range of about 1.degree. F. to about 20.degree. F. per minute. ### Claim 10 (depends on 9) The process in accordance with claim 9, wherein said rate is about 7.degree. F. per minute. ### Claim 11 (depends on 7) The process in accordance with claim 7, wherein said hydro-thermal calcining further comprises maintaining said first target temperature for a time of less than about 5 hours. ### Claim 12 (depends on 11) The process in accordance with claim 11, wherein said time is within the range of about 1-3 hours. ### Claim 13 (depends on 12) The process in accordance with claim 12, wherein said hydro-thermal calcining further comprises increasing the temperature of said aggregate to a second target temperature higher than said first target temperature but less than about 1400.degree. F. ### Claim 14 (depends on 13) The process in accordance with claim 13, wherein said second target temperature is within the range of about 1000.degree. F. to about 1200.degree. F. ### Claim 15 (depends on 14) The process in accordance with claim 14, wherein said increasing said temperature of said aggregate to said second target temperature comprises increasing the temperature of said aggregate from said first target temperature at a rate within the range of about 1.degree. F. to about 20.degree. F per minute. ### Claim 16 (depends on 15) The process in accordance with claim 15, wherein said rate is about 7.degree. F. minute. ### Claim 17 (depends on 15) The process in accordance with claim 15, wherein said hydro-thermal calcining further comprises maintaining said second target temperature for a time of less than about 12 hours. ### Claim 18 (depends on 17) The process in accordance with claim 17, wherein said time is for about 4 hours. ### Claim 19 (depends on 14) The process in accordance with claim 14, wherein said humid atmosphere during said hydro-thermally calcining comprises a volume percent water within the range of 30% to 100%. ### Claim 20 (depends on 19) The process in accordance with claim 19, wherein said volume percent water is within the range of about 50% to about 80%. ### Claim 21 (depends on 1) The process in accordance with claim 1, wherein said water is deionized water. ### Claim 22 (depends on 21) The process in accordance with claim 21, wherein said rinsing is continued until the pH of effluent water is reduced to a pH within the range of about 10-11. ### Claim 23 (depends on 22) The process of claim 22, wherein said pH of effluent water is within the range of about 10.5 to about 10.8. ### Claim 24 (depends on 1) The process in accordance with claim 1, wherein said aqueous solution of base and said water medium are at temperatures ranging from ambient up to about 212.degree. F. ### Claim 25 (depends on 1) The process in accordance with claim 1, wherein said aqueous solution of base and said water have temperatures within the range of about 50.degree. F. to about 90.degree. F. ### Claim 26 (depends on 1) The process in accordance with claim 1, wherein said basic aqueous solution of base comprises a substances for neutralizing acidity in said hydro-thermally calcined aggregate. ### Claim 27 (depends on 26) The process in accordance with claim 26, wherein said aqueous solution of base comprises a member selected from the group consisting of solutions containing basic salts of chelating agents. ### Claim 28 (depends on 26) The process in accordance with claim 26, wherein said aqueous solution of base comprises a solution containing at least one member selected form the group consisting of potassium hydroxide, sodium hydroxide, barium hydroxide, lithium hydroxide, rubidium hydroxide, and cesium hydroxide. ### Claim 29 (depends on 27) The process in accordance with claim 27, wherein said solutions of basic salts of chelating agents comprise basic salts of amino polycarboxylic acids. ### Claim 30 (depends on 29) The process in accordance with claim 29, wherein said solutions of basic salts of amino polycarboxylic acids are selected from the group consisting of solutions of basic salts of nitrilotriacetic acid and basic salts of ethylenediaminetetraacetic acid. ### Claim 31 (depends on 30) The process in accordance with claim 30, wherein said solutions of basic salts of amino polycarboxylic acids comprise solutions of basic salts of thylenediaminetetraacetic acid. ### Claim 32 (depends on 31) The process in accordance with claim 31, wherein said solutions of basic salts of ethylenediaminetetraacetic acid are selected from the group consisting of potassium ethylenediaminetetraacetic acid and sodium ethylenediaminetetraacetic acid, and potassium salts of ethylenediaminetetraacetic acid and sodium salts of ethylenediaminetetraacetic acid. ### Claim 33 (depends on 27) The process in accordance with claim 27 wherein said zeolite comprises a cation and said aqueous solution of base comprises a cation which is the same cation as said cation of said zeolite. ### Claim 34 (depends on 33) The process in accordance with claim 33, wherein said aqueous solution of base comprises a KOH solution. ### Claim 35 (depends on 27) The process in accordance with claim 27, wherein said aqueous solution of base has a concentration within the range of about 0.01 to 1.0 normal. ### Claim 36 (depends on 35) The process in accordance with claim 35, wherein said washing comprises exposing said hydro-thermally calcined aggregates to an amount of said aqueous solution of base in the range of about 1.0 to 5.0 times the weight of said calcined aggregates. ### Claim 37 (depends on 36) The process in accordance with claim 36, wherein said washing is performed for a time within the range of about 5 minutes to about 60 minutes. ### Claim 38 (depends on 1) The process in accordance with claim 1, further comprising drying said washed aggregate. ### Claim 39 (depends on 1) The process in accordance with claim 1, further comprising post curing said washed aggregate. ### Claim 40 (depends on 39) The process in accordance with claim 39, wherein said post curing comprises subjecting said aggregate to post curing temperatures within a range of about 180.degree. F. to about 250.degree. F. ### Claim 41 (depends on 40) The process in accordance with claim 40, wherein said post curing at said post curing temperatures is performed for a post curing time within a range of about 1 to about 20 hours. ### Claim 42 (depends on 41) The process in accordance with claim 41, wherein said post curing is performed under a humid atmosphere. ### Claim 43 (depends on 42) The process in accordance with claim 42, wherein said humid atmosphere comprises a volume percent water within the range of about 40% to about 100%. ### Claim 44 (depends on 39) The process in accordance with claim 39, further comprising post hydro-thermally calcining said post cured aggregate. ### Claim 45 (depends on 44) The process in accordance with claim 44, wherein said post hydro-thermal calcining comprises subjecting said post cured aggregate to a humid atmosphere at elevated post hydro-thermally calcining temperatures and for times which are sufficient to strengthen, harden, and passivate said post cured aggregate without blocking access to micropores in said zeolite or causing permanent structural change to said zeolite. ### Claim 46 (depends on 45) The process in accordance with claim 45, wherein said post hydro-thermal calcining temperatures are less than about 1400.degree. F. ### Claim 47 (depends on 46) The process in accordance with claim 46, wherein said post hydro-thermal calcining comprises raising the temperature of said post cured aggregate to a first post hydro-thermally calcining target temperature within a range of about 400.degree. F. to about 700.degree. F. ### Claim 48 (depends on 47) The process in accordance with claim 47, wherein said post hydro-thermal calcining further comprises increasing the temperature of said post cured aggregate to a second post hydro-thermally calcining target temperature higher than said first target temperature but less than about 1400.degree. F. ### Claim 49 (depends on 48) The process in accordance with claim 48, wherein said increasing said temperature of said post cured aggregate comprises increasing the temperature of said post cured aggregate from an initial temperature and from said first hydro-thermally calcining target temperature at a rate within the range of about 1.degree. F. to about 20.degree. F. per minute. ### Claim 50 (depends on 49) The process in accordance with claim 49, wherein said humid atmosphere comprises a volume percent water within the range of 40% to 100%. ### Claim 51 (depends on 1) The process in accordance with claim 1, wherein said aggregate comprises inorganic oxide containing aluminum comprising a source of alumina. ### Claim 52 (depends on 51) The process in accordance with claim 51, wherein said source of alumina comprises hydrated alumina. ### Claim 53 (depends on 50) The process in accordance with claim 50, wherein said hydrated alumina is a form of alumina selected from the group consisting of commercial grades of alumina. ### Claim 54 (depends on 53) The process in accordance with claim 53, wherein said commercial grades of alumina are selected from the group consisting of boehmite and mixtures of boehmite and pseudo boehmite. ### Claim 55 (depends on 52) The process in accordance with claim 52, wherein said alumina has a particle size within the range of about 10 to about 100 microns. ### Claim 56 (depends on 55) The process in accordance with claim 55, wherein said alumina has an average particle size of about 65 microns. ### Claim 57 (depends on 56) The process in accordance with claim 56, wherein said aggregate comprises a peptizing agent selected from the group consisting of substances having a pH of less than or equal to 4.0 and substances having a pH of greater than or equal to 10.0. ### Claim 58 (depends on 57) The process in accordance with claim 57, wherein said peptizing agent is an acidic substance. ### Claim 59 (depends on 58) The process in accordance with claim 58, wherein said acidic substance is a member selected from the group consisting of an acid, an acidic alumina sol, aluminum chloride and aluminum bromide. ### Claim 60 (depends on 59) The process in accordance with claim 59, wherein said acidic substance is an acid. ### Claim 61 (depends on 60) The process in accordance with claim 60, wherein said acid is selected from the group consisting of organic acids, hydrochloric acid, perchloric acid, hydrobromic acid, and nitric acid. ### Claim 62 (depends on 61) The process in accordance with claim 61, wherein said organic acids are selected from the group consisting of acetic acid, formic acid, proprionic acid, oxalic acid, citric acid, trichloroacetic acid, and chloracetic acid. ### Claim 63 (depends on 61) The process in accordance with claim 61, wherein said acid is nitric acid. ### Claim 64 (depends on 63) The process in accordance with claim 63, wherein said nitric acid is present in an amount within the range of about 0.5% to about 3.0% by weight of said aggregate. ### Claim 65 (depends on 1) The process in accordance with claim 1, wherein said zeolite is selected from the crystalline alumina silicates represented by the following general formula expressed in terms of moles: 0.9.+-.0.2M.sub.2 /.sub.n O:Al.sub.2 O.sub.3 :XSiO.sub.2 wherein M is selected from the group consisting of metal cations and hydrogen, N is its valence and X is a number from about 1.5 to about 200. ### Claim 66 (depends on 65) The process in accordance with claim 65, wherein said zeolites are selected from the group consisting of mordenite, zeolite X, zeolite Y, mazzite, zeolite L, ZSM-5, zeolite beta, zeolite rho, ZK5, titanosilicate, ZSM-5 containing phosphorous, and zeolites having a silicon-aluminum ratio within the range of about 10:1 to 100:1. ### Claim 67 (depends on 66) The process in accordance with claim 66, wherein said zeolites are large pore zeolites. ### Claim 68 (depends on 67) The process in accordance with claim 67, wherein said large pore zeolite are selected from the group consisting of mordenite, zeolite X, zeolite Y, mazzite, and zeolite L. ### Claim 69 (depends on 68) The process in accordance with claim 68, wherein said large pore zeolite is zeolite L. ### Claim 70 (depends on 69) The process in accordance with claim 69, wherein said zeolite L has a pH within the range of about 9.4 to about 10.0. ### Claim 71 (depends on 69) The process in accordance with claim 69, wherein said zeolite L comprises highly crystalline crystallites wherein at least 50% of said crystallites are in the form of distinct circular disc-shaped cylinders with an aspect ratio of less than about 0.5 and with a mean diameter of at least 0.2 micron. ### Claim 72 (depends on 71) The process in accordance with claim 71, wherein at least 70% of said crystallites are in the form of said cylinders. ### Claim 73 (depends on 69) The process in accordance with claim 69, wherein said zeolite L comprises at least one cation selected from the group consisting of potassium, sodium, strontium, barium, calcium, cobalt, lithium, magnesium, rubidium, iron, cesium and mixtures of one or more members selected from the group consisting of potassium, sodium, strontium, barium, calcium, cobalt, lithium, magnesium, rubidium, iron, cesium. ### Claim 74 (depends on 73) The process in accordance with claim 73, wherein said cation is at least one member selected from the group consisting of potassium and barium. ### Claim 75 (depends on 74) The process in accordance with claim 74, wherein said cation is potassium. ### Claim 76 (depends on 1) The process in accordance with claim 1, further comprising loading said hydro-thermally calcined aggregate after said washing with at least one metal selected from the group of Group IB metals, Group VII metals, Group VIII metals, tin, germanium and tungsten. ### Claim 77 (depends on 76) The process in accordance with claim 76, wherein said at least one metal is a Group VIII metal. ### Claim 78 (depends on 77) The process in accordance with claim 77, wherein said Group VIII metal is platinum. ### Claim 79 (depends on 78) The process in accordance with claim 78, wherein said platinum is present in an amount within the range of about 0.3 to 1.5 wt. % of said aggregate. ### Claim 80 (depends on 79) The process in accordance with claim 79, wherein at least 75-95% by weight of said platinum is dispersed within pores of said zeolite L. ### Claim 81 (depends on 1) The process in accordance with claim 1, wherein said aggregate is a member selected from the group consisting of agglomerates, pellets, pills, prills, spheres, tablets and extrudates. ### Claim 82 (depends on 81) The process in accordance with claim 81, further comprising forming said paste into an extrudate. ### Claim 83 A process for producing aggregates of zeolite comprising: a) combining a source of alumina with zeolite to form a uniform mixture comprising alumina and zeolite; b) adding a peptizing agent and water to form a resultant mixture comprising alumina, zeolite, peptizing agent and water; c) preparing said resultant mixture into a paste having a consistency suitable for forming, said paste comprising alumina, zeolite, peptizing agent and water; d) forming said paste into an aggregate; e) curing said aggregate to result in a cured aggregate; f) hydro-thermally calcining said cured aggregate to result in a hydro-thermally calcined aggregate; g) washing said calcined aggregate with a washing medium to result in a washed aggregate; h) rinsing said washed aggregate with a rinsing medium to result in a rinsed aggregate; and i) subjecting said rinsed aggregate to a treatment which removes said rinsing medium from said rinsed aggregate. ### Claim 84 (depends on 83) The process in accordance with claim 83, wherein said uniform mixture comprising zeolite and a source of alumina is essentially devoid of extraneously added water and has a moisture content provided essentially by water present in said zeolite and adsorbed on said alumina. ### Claim 85 (depends on 84) The process in accordance with claim 84, wherein said source of alumina is an inorganic oxide containing aluminum. ### Claim 86 (depends on 85) The process in accordance with claim 85, wherein said inorganic oxide comprises hydrates of alumina. ### Claim 87 (depends on 86) The process in accordance with claim 86, wherein said hydrates of alumina are members selected from the group consisting of boehmite, and a mixture of boehmite and pseudo-boehmite. ### Claim 88 (depends on 87) The process in accordance with claim 87, wherein said alumina is in the form of particles having a particle size within the range of about 10 to about 100 microns. ### Claim 89 (depends on 88) The process in accordance with claim 88, wherein said alumina has an average particle size of about 65 microns. ### Claim 90 (depends on 84) The process in accordance with claim 84, wherein said the step of adding said peptizing agent comprises blending said peptizing agent with said uniform mixture of alumina and zeolite under intense mixing conditions. ### Claim 91 (depends on 90) The process in accordance with claim 90, wherein said blending is performed in an intensive mixer. ### Claim 92 (depends on 91) The process in accordance with claim 91, wherein said blending said peptizing agent comprises distributing said peptizing agent substantially evenly into said mixture. ### Claim 93 (depends on 92) The process in accordance with claim 92, wherein said distributing is performed so as to substantially avoid forming zones in said mixture having relatively higher concentrations of said peptizing agent to result in said resultant mixture having a substantially uniform distribution of said peptizing agent. ### Claim 94 (depends on 93) The process in accordance with claim 93, wherein said uniform distribution of said peptizing agent is effected by intensely mixing said peptizing agent into said mixture for less than about 2 minutes after the initial addition of the peptizing agent into said mixture. ### Claim 95 (depends on 90) The process in accordance with claim 90, wherein said peptizing agent is selected from the group of substances consisting of substances having a pH of less than or equal to 4.0 and substances having a pH of greater than or equal to 10.0. ### Claim 96 (depends on 95) The process in accordance with claim 95, wherein peptizing agent is an acidic substance. ### Claim 97 (depends on 96) The process in accordance with claim 96, wherein said acidic substance is selected from the group consisting of an acid, an acid sol, aluminum chloride, and aluminum bromide. ### Claim 98 (depends on 97) The process in accordance with claim 97, wherein said acid substance is an acid. ### Claim 99 (depends on 98) The process in accordance with claim 98, wherein said acid is an organic acid selected from the group consisting of acetic acid, formic acid, oxalic acid, citric acid, trichloroacetic acid, and proprionic acid. ### Claim 100 (depends on 98) The process in accordance with claim 98, wherein said acid is nitric acid in an amount within the range of about 0.5 to about 2.0% by weight on a dry basis. ### Claim 101 (depends on 95) The process in accordance with claim 95, wherein said peptizing agent is a basic substance. ### Claim 102 (depends on 101) The process in accordance with claim 101, wherein said zeolite comprises a cation and said peptizing agent comprises a cation which is the same cation as said cation of said zeolite. ### Claim 103 (depends on 101) The process in accordance with claim 101, wherein said basic substance is KOH. ### Claim 104 (depends on 88) The process in accordance with claim 88, wherein said aggregate has an alumina content within the range of about 25% to 70% on a dry weight basis. ### Claim 105 (depends on 104) The process in accordance with claim 104, wherein said aggregate has an alumina content within the range of about 25% to 35% on a dry weight basis. ### Claim 106 (depends on 94) The process in accordance with claim 94, wherein said step of preparing said paste comprises mixing said resultant mixture for a period of time for a total mixing time after said initial addition of peptizing agent of less than about 15 minutes. ### Claim 107 (depends on 106) The process in accordance with claim 106, wherein said total mixing time is less than about 5 minutes. ### Claim 108 (depends on 106) The process in accordance with claim 106, wherein said consistency of said paste is suitable for extrusion and said forming comprises extruding said paste into an extrudate. ### Claim 109 (depends on 108) The process in accordance with claim 108, wherein said curing comprises subjecting said extrudate to temperatures within a range of about 180.degree. F. to about 250.degree. F. ### Claim 110 (depends on 109) The process in accordance with claim 109, wherein said curing at said temperatures is performed for a time within a range of about 1 to about 20 hours. ### Claim 111 (depends on 109) The process in accordance with claim 109, wherein said curing is performed under a humid atmosphere. ### Claim 112 (depends on 111) The process in accordance with claim 111, wherein said humid atmosphere comprises a volume percent water within the range of about 40% to about 100%. ### Claim 113 (depends on 109) The process in accordance with claim 109, wherein said hydro-thermally calcining comprises subjecting said cured extrudate to a humid atmosphere at elevated temperatures for times which are sufficient to strengthen, harden, and passivate said cured extrudate without blocking access to micropores of said zeolite or causing permanent structural change to said zeolite. ### Claim 114 (depends on 113) The process in accordance with claim 113, wherein said temperatures are less than about 1400.degree. F. ### Claim 115 (depends on 114) The process in accordance with claim 114, wherein said times are less than about 15 hours. ### Claim 116 (depends on 112) The process in accordance with claim 112, wherein said hydro-thermally calcining comprises raising the temperature of said extrudate to a first target temperature within a range of about 400.degree. F. to about 700.degree. F. ### Claim 117 (depends on 116) The process in accordance with claim 116, wherein said hydro-thermally calcining further comprises maintaining said first target temperature for a time of less than about 5 hours. ### Claim 118 (depends on 117) The process in accordance with claim 117, wherein said time is within the range of about 1-3 hours. ### Claim 119 (depends on 116) The process in accordance with claim 116, wherein said hydro-thermally calcining further comprises increasing the temperature of said extrudate to a second target temperature higher than said first target temperature but less than about 1400.degree. F. ### Claim 120 (depends on 119) The process in accordance with claim 119, wherein said second target temperature is within the range of about 1000.degree. F. and 1200.degree. F. ### Claim 121 (depends on 120) The process in accordance with claim 120, wherein said increasing said temperature of said extrudate comprises increasing the temperature of said extrudate from an initial temperature to said target temperatures at a rate within the range of about 1.degree. F. and 20.degree. F. per minute. ### Claim 122 (depends on 121) The process in accordance with claim 121, wherein said rate is about 7.degree. F. minute. ### Claim 123 (depends on 121) The process in accordance with claim 121, wherein said hydro-thermally calcining further comprises maintaining said second target temperature for a time of less than about 12 hours. ### Claim 124 (depends on 123) The process in accordance with claim 123, wherein said time is about 4 hours. ### Claim 125 (depends on 115) The process in accordance with claim 115, wherein said humid atmosphere comprises a volume percent water within the range of 40% to 100%. ### Claim 126 (depends on 125) The process in accordance with claim 125, wherein said volume percent water is within the range of about 60% to about 80%. ### Claim 127 (depends on 109) The process in accordance with claim 109, wherein said washing medium comprises a substance for dissolving detrital alumina from said extrudate. ### Claim 128 (depends on 127) The process of claim 127, wherein said washing comprises rinsing said washed aggregate with a rinsing medium. ### Claim 129 (depends on 128) The process in accordance with claim 128, wherein said rinsing medium is water. ### Claim 130 (depends on 129) The process in accordance with claim 129, wherein said rinsing is continued until the pH of effluent water is reduced to a pH within the range of about 10-11. ### Claim 131 (depends on 130) The process of claim 130, wherein said pH of effluent water is within the range of about 10.5 to about 10.8. ### Claim 132 (depends on 128) The process in accordance with claim 128, wherein said washing medium and said rinsing medium are at temperatures ranging from ambient up to about 212.degree. F. ### Claim 133 (depends on 128) The process in accordance with claim 128, wherein said washing medium and said rinsing medium have temperatures within the range of about 50.degree. F. to about 90.degree. F. ### Claim 134 (depends on 127) The process in accordance with claim 127, wherein said washing medium comprises a substance for neutralizing acidity in said alumina. ### Claim 135 (depends on 134) The process in accordance with claim 134, wherein said washing medium is a member selected from the group consisting of solutions of base and solutions containing basic salts of chelating agents. ### Claim 136 (depends on 135) The process in accordance with claim 135, wherein said washing medium is a solution of base. ### Claim 137 (depends on 133) The process in accordance with claim 133, wherein said solution of base is a solution containing at least one member selected form the group consisting of potassium hydroxide, sodium hydroxide, barium hydroxide, lithium hydroxide, rubidium hydroxide, and cesium hydroxide. ### Claim 138 (depends on 135) The process in accordance with claim 135, wherein said solutions of basic salts of chelating agents comprise basic salts of amino polycarboxylic acids. ### Claim 139 (depends on 138) The process in accordance with claim 138, wherein said solutions of basic salts of amino polycarboxylic acids are selected from the group consisting solutions of basic salts of nitrilotriacetic acid and basic salts of ethylenediaminetetraacetic acid. ### Claim 140 (depends on 139) The process in accordance with claim 139, wherein said solutions are solutions of basic salts of ethylenediaminetetraacetic acid. ### Claim 141 (depends on 140) The process in accordance with claim 140, wherein said solutions of basic salts of ethylenediaminetetraacetic acid are selected from the group consisting of potassium ethylenediaminetetraacetic acid and sodium ethylenediaminetetraacetic acid, and potassium salts of ethylenediaminetetraacetic acid and sodium salts of ethylenediaminetetraacetic acid. ### Claim 142 (depends on 135) The process in accordance with claim 135, wherein said zeolite comprises a cation and said washing medium comprises a cation which is the same action as said cation of said zeolite. ### Claim 143 (depends on 142) The process in accordance with claim 142, wherein said cation is potassium and said washing medium is a KOH solution. ### Claim 144 (depends on 136) The process in accordance with claim 136, wherein said solution of base is within the range of about 0.01 to 1.0 normal. ### Claim 145 (depends on 144) The process in accordance with claim 144, wherein said washing comprises exposing said extrudates to an amount of said solution of base in the range of about 1.0 to 5.0 times the weight of said calcined aggregates. ### Claim 146 (depends on 142) The process in accordance with claim 142, wherein said washing is performed for a time within the range of about 5 minutes to about 60 minutes. ### Claim 147 (depends on 108) The process in accordance with claim 108, further comprising drying said washed extrudate. ### Claim 148 (depends on 108) The process in accordance with claim 108, further comprising post curing said washed extrudate. ### Claim 149 (depends on 148) The process in accordance with claim 148, further comprising post hydro-thermally calcining said cured extrudate. ### Claim 150 (depends on 108) The process in accordance with claim 108, further comprising loading said hydro-thermally calcined extrudate after said washing with at least one metal selected from the group of Group IB metals, Group VII metals, Group VIII metals, tin, germanium and tungsten. ### Claim 151 (depends on 150) The process in accordance with claim 150, wherein said at least one metal is a Group VIII metal. ### Claim 152 (depends on 151) The process in accordance with claim 151, wherein said Group VIII metal is platinum. ### Claim 153 (depends on 152) The process in accordance with claim 152, wherein said platinum is present in an amount within the range of about 0.3 to 1.5 wt. % of said aggregate. ### Claim 154 (depends on 152) The process in accordance with claim 152, wherein at least 75%-95% by weight of said platinum is dispersed within pores of said zeolite L. ### Claim 155 An aggregate comprising: an inorganic metal oxide and zeolite crystals having micropores bound into an aggregate, said aggregate having an exterior surface with openings and interstitial spaces communicating by said openings with said exterior surface and said micropores wherein said aggregate exhibits the following characteristics: i) a crush strength greater than about 0.9 pound per millimeter; ii) a loss by attrition resistance of less than about 3.0%. ### Claim 156 (depends on 155) The aggregate of claim 155, wherein said crush strength is greater than about 1.25 pounds per millimeter. ### Claim 157 (depends on 155) The aggregate of claim 155, wherein said loss by attrition resistance is about 2.0%. ### Claim 158 (depends on 155) The aggregate of claim 155, wherein said inorganic metal oxide comprises hydrated alumina. ### Claim 159 (depends on 158) The process in accordance with claim 158, wherein said hydrated alumina is selected from commercial grades of alumina. ### Claim 160 (depends on 159) The aggregate of claim 159, wherein said commercial grades of alumina are selected from the group consisting of boehmite and mixtures of boehmite and pseudoboehmite. ### Claim 161 (depends on 160) The aggregate of claim 160, wherein said alumina has a particle size within the range of about 10 to about 100 microns. ### Claim 162 (depends on 161) The aggregate of claim 161, wherein said alumina has an average particle size of about 65 microns. ### Claim 163 (depends on 161) The aggregate of claim 161, wherein said amount of alumina is within the range of about 25% to about 35%. ### Claim 164 (depends on 155) The aggregate of claim 155, wherein said zeolite is selected from the group consisting of mordenite, zeolite X, zeolite Y, mazzite, zeolite L, ZSM-5, zeolite beta, zeolite rho, ZK5, titanosilicate, ZSM-5 containing phosphorous, and zeolite having a silicon-aluminum ratio within the range of about 1.5:1 to 200:1. ### Claim 165 (depends on 164) The aggregate of claim 164, wherein said zeolites are large pore zeolites. ### Claim 166 (depends on 164) The aggregate of claim 164, wherein said large pore zeolite is zeolite L. ### Claim 167 (depends on 166) The aggregate of claim 166, wherein said zeolite L has a pH within the range of about 9.4 to about 10.0. ### Claim 168 (depends on 166) The aggregate of claim 166, wherein said zeolite L comprises highly crystalline crystallites wherein at least 50% of said crystallites are in the form of distinct circular disc-shaped cylinders with an aspect ratio of less than about 0.5 and with a mean diameter of at least 0.2 micron. ### Claim 169 (depends on 166) The aggregate of claim 166, wherein said zeolite L comprises at least one cation selected from the group consisting of potassium, sodium, strontium, barium, calcium, cobalt, lithium, magnesium, rubidium, iron, cesium and mixtures of one or more members selected from the group consisting of potassium, sodium, strontium, barium, calcium, cobalt, lithium, magnesium, rubidium, iron, cesium. ### Claim 170 (depends on 169) The aggregate of claim 169, wherein said cation is at least one member selected from the group consisting of potassium and barium. ### Claim 171 (depends on 170) The aggregate of claim 170, wherein said cation is potassium. ### Claim 172 (depends on 155) The aggregate of claim 155, wherein said aggregate is a catalyst further comprising at least one metal selected from the group of Group IB metals, Group VII metals, Group VIII metals, tin, germanium and tungsten, and exhibits a catalyst activity pass through to said zeolite bound in said aggregate of about 70% of catalyst activity of said zeolite. ### Claim 173 (depends on 163) The aggregate of claim 163, wherein said at least one metal is a Group VIII metal. ### Claim 174 (depends on 173) The aggregate of claim 173, wherein said Group VIII metal is platinum. ### Claim 175 (depends on 174) The aggregate of claim 174, wherein said platinum is present in an amount within the range of about 0.3 to 1.5 wt.% of said aggregate. ### Claim 176 (depends on 174) The aggregate of claim 174, wherein at least 75% of said platinum is finely dispersed as particles having a size less than about 7 Angstrom units. ### Claim 177 (depends on 176) The aggregate of claim 176, wherein at least about 90% of said platinum is dispersed within said micropores of said zeolite. ### Claim 178 (depends on 155) The aggregate of claim 155, wherein said aggregate is an extrudate. ### Claim 179 An aggregate comprising: a) a metal oxide containing aluminum bound into an aggregate having an exterior surface and mesopores communicating by openings with said exterior surface; and b) zeolite crystals having micropores bound by said metal oxide into said aggregate, wherein said exterior surface of said aggregate and said zeolite are essentially devoid of substance which interferes with communication among said micropores, said mesopores, and said openings for conducting reactants and products between said exterior surface and said micropores. ### Claim 180 (depends on 179) The aggregate of claim 179, wherein said metal oxide containing aluminum is hydrated alumina. ### Claim 181 (depends on 180) The aggregate of claim 180, wherein said hydrated alumina is alumina selected from the group consisting of boehmite and mixtures of boehmite and pseudo boehmite. ### Claim 182 (depends on 181) The aggregate of claim 181, wherein said alumina has a particle size within the range of about 10 to about 100 microns. ### Claim 183 (depends on 182) The aggregate of claim 182, wherein said alumina has an average particle size of about 65 microns. ### Claim 184 (depends on 182) The aggregate of claim 182, wherein said alumina is present in an amount within the range of about 25% to about 35 % by total weight of said aggregate. ### Claim 185 (depends on 179) The aggregate of claim 179, wherein said zeolite is selected from the group consisting of mordenite, zeolite X, zeolite Y, mazzite, zeolite L, ZSM-5, zeolite beta, zeolite rho, ZK5, titanosilicate, ZSM-5 containing phosphorous, and zeolites having a silicon-aluminum ratio within the range of about 75:1 to 100:1. ### Claim 186 (depends on 185) The aggregate of claim 185, wherein said zeolites are large pore zeolites. ### Claim 187 (depends on 186) The aggregate of claim 186, wherein said large pore zeolite is zeolite L. ### Claim 188 (depends on 181) The aggregate of claim 181, wherein said zeolite L has a pH within the range of about 9.4 to about 10.0. ### Claim 189 (depends on 181) The aggregate of claim 181, wherein said zeolite L comprises highly crystalline crystallites wherein at least 50% of said crystallites are in the form of distinct circular disc-shaped cylinders with an aspect ratio of less than about 0.5 and with a mean diameter of at least 0.2 micron. ### Claim 190 (depends on 187) The aggregate of claim 187, wherein said zeolite L comprises at least one cation selected from the group consisting of potassium, sodium, strontium, barium, calcium, cobalt, lithium, magnesium, rubidium, iron, cesium and mixtures of one or more members selected from the group consisting of potassium, sodium, strontium, barium, calcium, cobalt, lithium, magnesium, rubidium, iron, cesium. ### Claim 191 (depends on 190) The aggregate of claim 190, wherein said cation is at least one member selected from the group consisting of potassium and barium. ### Claim 192 (depends on 191) The aggregate of claim 191, wherein said cation is potassium. ### Claim 193 (depends on 179) The aggregate of claim 179, wherein each metal selected from the group of Group IB metals, Group VII metals, Group VIII metals, tin, germanium and tungsten. ### Claim 194 (depends on 193) The aggregate of claim 193, wherein said at least one metal is a Group VIII metal. ### Claim 195 (depends on 194) The aggregate of claim 194, wherein said Group VIII metal is platinum. ### Claim 196 (depends on 175) The aggregate of claim 175, wherein said platinum is present in an amount within the range of about 0.3 to 1.5 wt. % of said aggregate. ### Claim 197 (depends on 195) The aggregate of claim 195, wherein at least 90% of said platinum is finely dispersed within said micropores. ### Claim 198 (depends on 179) The aggregate of claim 179, wherein said aggregate is an extrudate. ### Claim 199 (depends on 1) The product produced by the process of claim 1. ### Claim 200 (depends on 5) The product produced by the process of claim 5. ### Claim 201 (depends on 6) The product produced by the process of claim 6. ### Claim 202 (depends on 10) The product produced by the process of claim 10. ### Claim 203 (depends on 15) The product produced by the process of claim 15. ### Claim 204 (depends on 22) The product produced by the process of claim 22. ### Claim 205 (depends on 27) The product produced by the process of claim 27. ### Claim 206 (depends on 44) The product produced by the process of claim 44. ### Claim 207 (depends on 57) The product produced by the process of claim 57. ### Claim 208 (depends on 64) The product produced by the process of claim 64. ### Claim 209 (depends on 66) The product produced by the process of claim 66. ### Claim 210 (depends on 71) The product produced by the process of claim 71. ### Claim 211 (depends on 73) The product produced by the process of claim 73. ### Claim 212 (depends on 74) The product produced by the process of claim 74. ### Claim 213 (depends on 76) The product produced by the process of claim 76. ### Claim 214 (depends on 78) The product produced by the process of claim 78. ### Claim 215 (depends on 80) The product produced by the process of claim 80. ### Claim 216 (depends on 82) The product produced by the process of claim 82. ### Claim 217 (depends on 83) The product produced by the process of claim 83. ### Claim 218 (depends on 84) The product produced by the process of claim 84. ### Claim 219 (depends on 88) The product produced by the process of claim 88. ### Claim 220 (depends on 94) The product produced by the process of claim 94. ### Claim 221 (depends on 165) The product produced by the process of claim 165. ### Claim 222 (depends on 159) The product produced by the process of claim 159. ### Claim 223 (depends on 154) The product produced by the process of claim 154. ### Claim 224 A regenerable catalyst comprising: a catalyst metal dispersed in zeolite bound by a metal oxide containing aluminum binder into an aggregate, said regenerable catalyst exhibiting a level of regenerability, expressed as a ratio of the catalyst activity test rating of said catalyst as regenerated relative to the catalyst activity test rating of said catalyst in a fresh state prior to operation on oil, of at least 70%. ### Claim 225 (depends on 224) The regenerated catalyst of claim 224, wherein said level of regenerability is at least 80%. ### Claim 226 (depends on 225) The regenerable catalyst of claim 225, wherein said level of regenerability is at least 90%. ### Claim 227 (depends on 224) The regenerable catalyst of claim 224, wherein said zeolite has micropores, said aggregate has an exterior surface with opening and mesopores between particles of said binder and said zeolite, and wherein said exterior surface of said aggregate and said zeolite are essentially devoid of substance which interferes with communication among said micropores, said mesopores, and said openings for conducting reactants and products between said exterior surface and said micropores. ### Claim 228 (depends on 224) The regenerable catalyst of claim 224, wherein said regenerable catalyst exhibits: i) a crush strength of greater than about 0.9 pound per millimeter; ii) a loss by attrition resistance of less than about 3.0%; and iii) a catalyst activity pass through to said bound zeolite of at least about 70% of the initial catalyst activity of the zeolite. ### Claim 229 (depends on 224) The regenerable catalyst of claim 224, wherein said aggregate is formed by: a) providing a formable paste comprising said zeolite, said metal oxide containing aluminum, a peptizing agent and water; b) forming said paste into an aggregate; c) curing said aggregate to result in a cured aggregate; d) hydro-thermally calcining said cured aggregate to result in a hydro-thermally calcined aggregate; and e) washing said hydro-thermally calcined aggregate with a washing medium to result in a washed aggregate, before f) loading said aggregate with a catalytically active metal to result in said regenerable catalyst. ### Claim 230 (depends on 224) The regenerable catalyst of claim 224, wherein said metal oxide containing aluminum is hydrated alumina and said aggregate is formed by: a) combining said alumina with zeolite to form a uniform mixture comprising alumina and zeolite; b) adding a peptizing agent and water to form a resultant mixture comprising alumina, zeolite, peptizing agent and water; c) preparing said resultant mixture into a paste having a consistency suitable for forming, said paste comprising alumina, zeolite, peptizing agent and water; d) forming said paste into an aggregate; e) curing said aggregate to result in a cured aggregate; f) hydro-thermally calcining said cured aggregate to result in a calcined aggregate; g) washing said calcined aggregate with a washing medium to result in a washed aggregate; h) rinsing said washed aggregate with a rinsing medium to result in a rinsed aggregate; and i) subjecting said rinsed aggregate to a treatment which removes said rinsing medium from said rinsed aggregate, before j) loading said aggregate with a catalytically active metal to result in said regenerable catalyst. ### Claim 231 (depends on 224) The regenerable catalyst of claim 224, wherein said metal oxide containing aluminum is a hydrated alumina. ### Claim 232 (depends on 231) The regenerable catalyst of claim 231, wherein said hydrated alumina is selected from the group consisting of boehmite and mixtures of boehmite and pseudo boehmite. ### Claim 233 (depends on 232) The regenerable catalyst of claim 232, wherein said alumina has a particle size within the range of about 10 to about 100 microns. ### Claim 234 (depends on 233) The regenerable catalyst of claim 233, wherein said alumina has an average particle size of about 65 microns. ### Claim 235 (depends on 233) The regenerable catalyst of claim 233, wherein said zeolite is selected from the group consisting of mordenite, zeolite X, zeolite Y, mazzite, zeolite L, ZSM-5, zeolite beta, zeolite rho, ZK5, titanosilicate, ZSM-5 containing phosphorous, and zeolite having a silicon-aluminum ratio within the range of about 75:1 to 100:1. ### Claim 236 (depends on 235) The regenerable catalyst of claim 235, wherein said zeolite is a large pore zeolite. ### Claim 237 (depends on 236) The regenerated catalyst of claim 236, wherein said large pore zeolite is zeolite L. ### Claim 238 (depends on 237) The regenerable catalyst of claim 237, wherein said zeolite L comprises highly crystalline crystallites wherein at least 50% of said crystallites are in the form of distinct circular disc-shaped cylinders with an aspect ratio of less than about 0.5 and with a mean diameter of at least 0.2 micron. ### Claim 239 (depends on 237) The regenerable catalyst of claim 237, wherein said zeolite L has a pH within the range of about 9.4 to about 10.0. ### Claim 240 (depends on 237) The regenerated catalyst of claim 237, wherein said zeolite L comprises at least one cation selected from the group consisting of potassium, sodium, strontium, barium, calcium, cobalt, lithium, magnesium, rubidium, iron, cesium and mixtures of one or more members selected from the group consisting of potassium, sodium, strontium, barium, calcium, cobalt, lithium, magnesium, rubidium, iron, cesium. ### Claim 241 (depends on 237) The regenerable catalyst of claim 237, wherein said catalyst metal is at least one metal selected from the group of Group IB metals, Group VII metals, Group VIII metals, tin, germanium and tungsten. ### Claim 242 (depends on 241) The regenerable catalyst of claim 241, wherein said at least one metal is a Group VIII metal. ### Claim 243 (depends on 242) The regenerated catalyst of claim 242, wherein said Group VIII metal is platinum. ### Claim 244 (depends on 243) The regenerable catalyst of claim 243, wherein said platinum is present in an amount within the range of about 0.3 to 1.5 wt. % of said aggregate. ### Claim 245 (depends on 244) The regenerable catalyst of claim 244, wherein at least 75%-95% by weight of said platinum is dispersed within pores of said zeolite L. ### Claim 246 (depends on 224) The regenerable catalyst of claim 224, wherein said aggregate is a member selected from the group consisting of agglomerates, pellets, pills, prills, spheres, tablets and extrudates. ### Claim 247 (depends on 246) The regenerable catalyst of claim 246, wherein said aggregate an extrudate.