US4272409A
Expired / Lapsed
US
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Aluminosilicate sols and powders
Assignee: EIDP Inc
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Filing: 1979-10-12
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Granted: 1981-06-09
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Expires: 1999-10-12
Abstract
Abstract An amorphous aluminosilicate sol with uniform size particles and a porous amorphous aluminosilicate powder composition useful as a catalyst in petroleum cracking is prepared by a process comprising (1) preparing a sol of discrete colloidal particles of uniform size within the range of from 2 to 87 nanometers, the surface of the particles consisting of a coating of an aluminosilicate at least 0.5 nanometer in thickness, by separately and simultaneously adding a sol of silica or a solution of sodium or potassium silicate and a solution of sodium or potassium aluminate to a heel sol of uniform-sized colloidal particles of aluminosilicate, silica, or one or more refractory metal oxides at a certain rate of addition and at a constant pH in the range of 9 to 12 and a temperature of 50° to 100° C. to deposit or coat aluminosilicate onto the surface of the heel sol particles, (2) ion exchanging the sodium or potassium ions of the sol from (1) for ammonium ions, (3) optionally removing the ammonium ions partially or completely with one or more metal ions described herein selected from Groups I to VIII of the Periodic Table, and (4) removing water from the sol without gelling so that the particles become uniformly packed into aggregates having pores of substantially uniform size and coating said powder with a surface layer 0 to 15% by weight of a metal or metal oxide, said powder having a specific surface area of 30 to 750 m 2 /g, a bulk density of 0.5 g/cc or more and substantially uniform size pore diameters of from 20 A to 250 A, with pore diameters of 20 A to 45 A having a uniformity such that at least 90% of the pore volume is made up of pores of from 0.6 D to 1.4 D and pore diameters of 45 A to 250 A having a uniformity such that at least 80% of the pore volume is made up of pores of from 0.6 D to 1.4 D, where D is the median pore diameter.
Inventors
- 👤 Horacio E. Bergna
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 08:40
CPC Classifications
C; C10; C10G; C10G11/00; C10G11/02; C10G11/04; C10G11/05; B; B01; B01J; B01J35/00; B01J35/60; B01J37/00; B01J37/02; B01J37/024; B01J35/61; B01J35/613; B01J35/615; B01J35/617; B01J35/63; B01J35/633; B01J35/64; B01J35/647; B01J35/66; B01J35/67
Claims Analysis
Total Claims: 35
Claim 1
Independent Claim
312 words
A porous powder composition comprising porous aggregates of spheroidal particles of from 3 to 90 nanometers which particles are nonporous to nitrogen and contain: (a) a core of silica, aluminosilicate or one or more refractory metal oxides selected from alumina, zirconia, titania, thoria and rare earth oxides; (b) a coating around said core of at least 0.5 nanometer in depth of an amorphous hydrous aluminosilicate compound having a molar ratio of Si:Al of from 1:1 to 19:1 and comprising one or more cations selected from sodium, potassium, ammonium, hydrogen and Groups I to VIII metals selected from Cs, Li, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, La, Ce, rare earth metals, Hf, Ta, W, Re, Os, Ir, Pt, Au, Sn, Cd, Bi and Sb; and (c) a surface layer over said coating of 0 to 15% by weight of a metal or metal oxide selected from Cs, Li, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, La, Ce, rare earth metals, Hf, Ta, W, Re, Os, Ir, Pt, Au, Sn, Cd, Bi and Sb; said powder composition having a specific surface area of 30 to 750 m 2 /g, a bulk density of 0.5 g/cc or more and substantially uniform size pore diameters of from 20 A to 250 A, with pore diameters of 20 A to 45 A having a uniformity such that at least 90% of the pore volume is made up of pores of from 0.6 D to 1.4 D and pore diameters of 45 A to 250 A having a uniformity such that at least 80% of the pore volume is made up of pores of from 0.6 D to 1.4 D, where D is the median pore diameter.
Claim 2
Dependent Claim
312 words
A porous powder composition comprising porous aggregates of spheroidal particles of from 3 to 90 nanometers which particles are nonporous to nitrogen and contain: (a) a core of silica, aluminosilicate or one or more refractory metal oxides selected from alumina, zirconia, titania, thoria and rare earth oxides; (b) a coating around said core of at least 0.5 nanometer in depth of an amorphous hydrous aluminosilicate compound having a molar ratio of Si:Al of from 1:1 to 19:1 and comprising one or more cations selected from sodium, potassium, ammonium, hydrogen and Groups I to VIII metals selected from Cs, Li, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, La, Ce, rare earth metals, Hf, Ta, W, Re, Os, Ir, Pt, Au, Sn, Cd, Bi and Sb; and (c) a surface layer over said coating of 0 to 15% by weight of a metal or metal oxide selected from Cs, Li, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, La, Ce, rare earth metals, Hf, Ta, W, Re, Os, Ir, Pt, Au, Sn, Cd, Bi and Sb; said powder composition having a specific surface area of 30 to 750 m 2 /g, a bulk density of 0.5 g/cc or more and substantially uniform size pore diameters of from 20 A to 250 A, with pore diameters of 20 A to 45 A having a uniformity such that at least 90% of the pore volume is made up of pores of from 0.6 D to 1.4 D and pore diameters of 45 A to 250 A having a uniformity such that at least 80% of the pore volume is made up of pores of from 0.6 D to 1.4 D, where D is the median pore diameter.
Claim 3
Dependent Claim
27 words
The composition of claim 1 wherein the refractory metal oxides of the core are selected from the group consisting of alumina, zirconia, titania, and rare earth oxides.
Claim 4
Dependent Claim
10 words
The composition of claim 1 wherein the core is aluminosilicate.
Claim 5
Dependent Claim
10 words
The composition of claim 1 wherein the core is silica.
Claim 6
Dependent Claim
16 words
The composition of claim 1 characterized by having a bulk density of 0.5 to 0.9 g/cc.
Claim 7
Dependent Claim
24 words
The composition of claim 1 in which the aggregates are spheroidal with an average diameter within the range of 5 to about 200 microns.
Claim 8
Dependent Claim
25 words
The composition of claim 1 wherein the cation of the aluminosilicate coating is selected from ammonium and hydrogen and the Group I to VIII metals.
Claim 9
Dependent Claim
18 words
The composition of claim 1 wherein the cations of the aluminosilicate coating are selected from ammonium and hydrogen.
Claim 10
Dependent Claim
14 words
The composition of claim 1 wherein the cation of the aluminosilicate coating is hydrogen.
Claim 11
Dependent Claim
32 words
The composition of claim 1 wherein, in the range of 20 A to 150 A pore diameters, 90% of the pore volume is of pores of from 0.6 D to 1.4 D.
Claim 12
Dependent Claim
32 words
The composition of claim 1 wherein, in the range of 45 A to 250 A pore diameters, 80% of the pore volume is of pores of from 0.6 D to 1.4 D.
Claim 13
Dependent Claim
21 words
The composition of claim 10 wherein 90% of the pore volume is of pores of from 0.7 D to 1.3 D.
Claim 14
Dependent Claim
36 words
The composition of claim 1 wherein the cation of Groups I to VIII are selected from the group consisting of Ca, Mg, Mn, Ru, Rh, Pd, La, W, Re, Ir, Pt, Ce and rare earth metals.
Claim 15
Dependent Claim
22 words
The composition of claim 1 wherein the metal or metal oxide coating is 1 to 8 % by weight of the powder.
Claim 16
Dependent Claim
14 words
The composition of claim 1 wherein the metal or metal oxide coating is 0%.
Claim 17
Dependent Claim
15 words
The composition of claim 1 wherein the ratio of Si:Al is from 1:1 to 6:1.
Claim 18
Dependent Claim
15 words
The composition of claim 1 wherein the ratio of Si:Al is from 3.5:1 to 6:1.
Claim 19
Dependent Claim
39 words
The composition of claim 1 wherein the metal or metal oxide surface layer is selected from the group consisting of Ca, Mg, Mn, Ru, Rh, Pd, La, W, Re, Ir, Pt, Ce, the rare earth metals and mixtures thereof.
Claim 20
Dependent Claim
36 words
The porous powder composition of claim 1 uniformly mixed with a crystalline aluminosilicate zeolite such that the mixture is 5 to 50% by weight crystalline aluminosilicate zeolite and 95 to 50% by weight of said powder.
Claim 21
Dependent Claim
36 words
The porous powder composition of claim 1 uniformly mixed with a crystalline aluminosilicate zeolite such that the mixture is 10 to 25% by weight crystalline aluminosilicate zeolite and 90 to 75% by weight of said powder.
Claim 22
Dependent Claim
353 words
A method for the preparation of the composition of claim 1 comprising: (a) preparing a heel sol of discrete colloidal particles selected from sodim, potassium or ammonium aluminosilicate, silica, and one or more refractory oxides selected from alumina, zirconia, lanthana, thoria, titania are rare earth oxides, said particles having a substantially uniform diameter within the range of 2 to about 85 nanometers, said aluminosilicate having a molar ratio of Si:Al of from 1:1 to 19:1, the initial concentration in the heel sol of sodium, potassium, ammonium aluminosilicate or refractory metal oxide being at least 0.2% by weight, with the particles stabilized against aggregation in the pH range 9 to 12; (b) adding to said heel, separately but simultaneously, two feed solutions, one being a solution of sodium or potassium silicate having from one to 36 grams of silica per 100 cc, or a sol of silicic acid containing from 1 to 12% silica, the other being a solution of sodium or potassium aluminate containing from 1 to 15% alumina, said feed solutions being added in relative rates and proportions to maintain a constant molar ratio of Si:Al in the feed streams of from 1:1 to 19:1 with the rate of addition of silica not to exceed 10 grams of SiO 2 per 1000 square meters of total surface area of particles in the heel sol per hour; (c) maintaining the pH of the heel sol at a constant value between 9 and 12 by adding cation exchange resin in the hydrogen or ammonium form, maintaining the temperature of the heel sol at from 50° to 100° C. until the particles in the heel sol have attained an increase in diameter of at least 1 nanometer and a maximum size of 90 nanometers; (d) filtering the sol from (c) to remove the cation exchange resin and optionally adjusting the concentration of the resulting aluminosilicate sol to a solids content of up to 60% by weight; and (e) drying the resulting substantially gel-free sol of particles having an aluminosilicate surface to a powder by removing water at a rate at which no gelling will occur.
Claim 23
Dependent Claim
25 words
The method of claim 21 wherein the pH of the heel sol during the addition of the feed solutions is maintained between 10 and 10.5.
Claim 24
Dependent Claim
16 words
The method of claim 21 wherein the discrete colloidal particles of the heel sol are silica.
Claim 25
Dependent Claim
22 words
The method of claim 21 wherein the discrete colloidal particles of the heel sol are a sodium, potassium or ammonium aluminosilicate sol.
Claim 26
Dependent Claim
20 words
The method of claim 21 wherein the discrete colloidal particles of the heel sol are one or more refractory oxides.
Claim 27
Dependent Claim
25 words
The method of claim 21 wherein the refractory oxides in the heel sol are selected from the group consisting of alumina, zirconia, lanthana and titania.
Claim 28
Dependent Claim
20 words
The method of claim 21 wherein the sodium or potassium silicate solution is 15 to 25% by weight of silica.
Claim 29
Dependent Claim
31 words
The method of claim 21 wherein the sol from (d) is ion-exchanged to partly or completely replace the sodium or potassium ions by hydrogen or ammonium ions before the drying step.
Claim 30
Dependent Claim
71 words
The method of claim 28 wherein the hydrogen or ammonium ions are replaced, completely or in part, with one or more ions selected from the group Cs, Rb, Li, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, La, Ce, rare earth metals, Hf, Ta, W, Re, Os, Ir, Pt, Au, Bi, Cd, Sn, Sb and mixtures thereof.
Claim 31
Dependent Claim
69 words
The method of claim 28 wherein the dried composition after (e) is impregnated with a solution comprising one or more metal cations selected from Os, Rb, Li, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, No, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, La, Ce, rare earth metals, Hf, Ta, W, Re, Os, Ir, Pt, Au, Be, Cd, Sn and Sb and drying.
Claim 32
Dependent Claim
31 words
The method of claim 28 wherein metal cations are introduced by adding a solution of a metal salt to the sol from (d) with intensive agitation at the point of mixing.
Claim 33
Dependent Claim
34 words
The method of claim 28 wherein the ammonium ions are replaced, completely or in part, by exchanging the ammonium ions of the sol with metal ions on a sulfonic acid type ion exchange resin.
Claim 34
Dependent Claim
351 words
An amorphous aluminosilicate powder composition prepared by the process comprising (a) preparing a heel sol of discrete colloidal particles selected from sodium, potassium or ammonium aluminosilicate, silica, and one or more refractory oxides selected from alumina, zirconia, lanthana, thoria, titania and rare earth oxides, said particles having a substantially uniform diameter within the range of 2 to about 85 nanometers, said aluminosilicate having a molar ratio of Si:Al of from 1:1 to 19:1, the initial concentration in the heel sol of sodium, potassium, ammonium aluminosilicate or refractory metal oxide being at least 0.2% by weight, with the particles stabilized against aggregation in the pH range 9 to 12; (b) adding to said heel, separately but simultaneously, two feed solutions, one being a solution of sodium or potassium silicate having from one to 36 grams of silica per 100 cc, or a sol of silicic acid containing from 1 to 12% silica, the other being a solution of sodium or potassium aluminate containing from 1 to 15% alumina, said feed solutions being added in relative rates and proportions to maintain a constant molar ratio of Si:Al in the feed streams of from 1:1 to 19:1 with the rate of addition of silica not to exceed 10 grams of SiO 2 per 1000 square meters of total surface area of particles in the heel sol per hour; (c) maintaining the pH of the heel sol at a constant value between 9 and 12 by adding cation exchange resin in the hydrogen or ammonium form, maintaining the temperature of the heel sol at from 50° to 100° C. until the particles in the heel sol have attained an increase in diameter of at least 1 nanometer and a maximum size of 90 nanometers; (d) filtering the sol from (c) to remove the cation exchange resin and optionally adjusting the concentration of the resulting aluminosilicate sol to a solids content of up to 60% by weight; and (e) drying the resulting substantially gel-free sol of particles having an aluminosilicate surface to a powder by removing water at a rate at which no gelling will occur.
Claim 35
Dependent Claim
351 words
An amorphous aluminosilicate powder composition prepared by the process comprising (a) preparing a heel sol of discrete colloidal particles selected from sodium, potassium or ammonium aluminosilicate, silica, and one or more refractory oxides selected from alumina, zirconia, lanthana, thoria, titania and rare earth oxides, said particles having a substantially uniform diameter within the range of 2 to about 85 nanometers, said aluminosilicate having a molar ratio of Si:Al of from 1:1 to 19:1, the initial concentration in the heel sol of sodium, potassium, ammonium aluminosilicate or refractory metal oxide being at least 0.2% by weight, with the particles stabilized against aggregation in the pH range 9 to 12; (b) adding to said heel, separately but simultaneously, two feed solutions, one being a solution of sodium or potassium silicate having from one to 36 grams of silica per 100 cc, or a sol of silicic acid containing from 1 to 12% silica, the other being a solution of sodium or potassium aluminate containing from 1 to 15% alumina, said feed solutions being added in relative rates and proportions to maintain a constant molar ratio of Si:Al in the feed streams of from 1:1 to 19:1 with the rate of addition of silica not to exceed 10 grams of SiO 2 per 1000 square meters of total surface area of particles in the heel sol per hour; (c) maintaining the pH of the heel sol at a constant value between 9 and 12 by adding cation exchange resin in the hydrogen or ammonium form, maintaining the temperature of the heel sol at from 50° to 100° C. until the particles in the heel sol have attained an increase in diameter of at least 1 nanometer and a maximum size of 90 nanometers; (d) filtering the sol from (c) to remove the cation exchange resin and optionally adjusting the concentration of the resulting aluminosilicate sol to a solids content of up to 60% by weight; and (e) drying the resulting substantially gel-free sol of particles having an aluminosilicate surface to a powder by removing water at a rate at which no gelling will occur.
References Cited (Backward Citations)
US2688003A
Cited
US2974108A
Cited
US2941958A
Cited
US3252917A
Cited
US3346509A
Cited
US3312615A
Cited
US3766057A
Cited
US3782075A
Cited
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