US4582815A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Extrusion of silica-rich solids
Assignee: Mobil Oil AS
•
Filing: 1984-07-06
•
Granted: 1986-04-15
•
Expires: 2004-07-06
Abstract
Abstract The present invention is directed to a method for extruding silica-rich solids. The method comprises mixing silica-rich solids with water in an alkali metal base or basic salt followed by mulling and extruding and subsequently drying the extrudate whereby the dried extrudate has a crush strength superior to that of the prior art. The silica-rich solids can be silica alone, zeolite alone or a mixture thereof. The alkali metal can be sodium hydroxide. The invention is also directed to a product which has a special attribute in that they have sufficient integrity to withstand treatments with acids so that it is now possible to steam, acid extract, or calcine such extrudates. The catalyst can be used in hydrocarbon conversions such as hydrocracking, isomerization, hydrogenation, dehydrogenation, polymerization, reforming, catalytic cracking, or catalytic hydrocracking. The invention also relates to a method for extruding silica-rich solids which comprises substituting an alkali metal for hydrogen in silanol groups on outside surfaces of the silica-rich solids, mulling and extruding the substituted silica-rich solids and drying the extrudate whereby the dried extrudate has a crush strength superior to that of the prior art. The invention is also directed to a method for increasing the silica to metal ratio of a zeolite. The method comprises mixing silica-rich solids with water and an alkali metal base or basic salt, mulling and extruding the silica-rich mixture, drying the extrudate, ion exchanging the extrudate and recovering the catalyst which can be substantially metal free.
Inventors
- 👤 Emmerson Bowes
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 14:59
CPC Classifications
B; B01; B01J; B01J37/00; B01J37/0009; B01J20/00; B01J20/02; B01J20/10; B01J20/16; B01J20/18; B01J20/183; B01J29/00; B01J29/04; B01J29/06; B01J29/08; B01J29/084; B01J2229/00; B01J2229/30; B01J2229/42
Claims Analysis
Total Claims: 68
Claim 1
Independent Claim
101 words
A method for extruding silica-rich solids which comprises mixing the silica-rich solids with water and an alkali metal base or basic salt followed by mulling and extruding wherein the amount of water added being sufficient to have a total solids content of from 25 to 75 weight percent, the alkali metal compound being added in an amount of from 0.25 to 10 weight percent on a dry basis based on the total solids calculated as sodium hydroxide equivalent, and drying and calcining the extrudate, whereby the dried and calcined extrudate has a crush strength superior to that of the prior art.
Claim 2
Independent Claim
101 words
A method for extruding silica-rich solids which comprises mixing the silica-rich solids with water and an alkali metal base or basic salt followed by mulling and extruding wherein the amount of water added being sufficient to have a total solids content of from 25 to 75 weight percent, the alkali metal compound being added in an amount of from 0.25 to 10 weight percent on a dry basis based on the total solids calculated as sodium hydroxide equivalent, and drying and calcining the extrudate, whereby the dried and calcined extrudate has a crush strength superior to that of the prior art.
Claim 3
Dependent Claim
12 words
The method according to claim 1 wherein the silica-rich solid is silica.
Claim 4
Dependent Claim
14 words
The method according to claim 1 wherein the silica-rich solid is a zeolite material.
Claim 5
Dependent Claim
12 words
The method according to claim 1 wherein the silica-rich solid is ZSM-5.
Claim 6
Dependent Claim
19 words
The method according to claim 1 wherein the silica-rich solid is a mixture of silica and a crystalline aluminosilicate.
Claim 7
Dependent Claim
17 words
The method according to claim 5 wherein the crystalline aluminosilicate has a silica-to-alumina ratio greater than 100.
Claim 8
Dependent Claim
17 words
The method according to claim 1 wherein the silica-rich solid is a mixture of ZSM-5 and silica.
Claim 9
Dependent Claim
14 words
The method according to claim 1 wherein the alkali metal base is sodium hydroxide.
Claim 10
Dependent Claim
14 words
The method according to claim 4 wherein the alkali metal base is sodium hydroxide.
Claim 11
Dependent Claim
14 words
The method according to claim 6 wherein the alkali metal base is sodium hydroxide.
Claim 12
Dependent Claim
30 words
The product produced by the method according to claim 1 having a crush strength of at least 4 pounds for a 1/8 inch length having a diameter of 1/16th inch.
Claim 13
Dependent Claim
30 words
The product produced by the method according to claim 2 having a crush strength of at least 4 pounds for a 1/8 inch length having a diameter of 1/16th inch.
Claim 14
Dependent Claim
30 words
The product produced by the method according to claim 3 having a crush strength of at least 4 pounds for a 1/8 inch length having a diameter of 1/16th inch.
Claim 15
Dependent Claim
30 words
The product produced by the method according to claim 4 having a crush strength of at least 4 pounds for a 1/8 inch length having a diameter of 1/16th inch.
Claim 16
Dependent Claim
30 words
The product produced by the method according to claim 8 having a crush strength of at least 4 pounds for a 1/8 inch length having a diameter of 1/16th inch.
Claim 17
Dependent Claim
30 words
The product produced by the method according to claim 5 having a crush strength of at least 4 pounds for a 1/8 inch length having a diameter of 1/16th inch.
Claim 18
Dependent Claim
29 words
The product produced by the method according to claim 6 having a crush strength of at least 4 pounds for 1/8 inch length having a diameter of 1/16th inch.
Claim 19
Dependent Claim
29 words
The product produced by the method according to claim 7 having a crush strength of at least 4 pounds for 1/8 inch length having a diameter of 1/16th inch.
Claim 20
Dependent Claim
41 words
A method for increasing the silica-to-alumina ratio of a zeolite having an initial silica-to-alumina ratio of at least 3 which comprises the product of claim 5 treated so as to remove at least a portion of the aluminum from said zeolite.
Claim 21
Dependent Claim
12 words
The method according to claim 19 wherein said zeolite is zeolite Y.
Claim 22
Dependent Claim
11 words
The method according to claim 19 wherein said zeolite is ZSM-5.
Claim 23
Dependent Claim
11 words
The method according to claim 19 wherein said zeolite is Beta.
Claim 24
Dependent Claim
24 words
The method according to claim 1, wherein the alkali metal base is a hydroxide of Group I metals of the Periodic Table of Elements.
Claim 25
Dependent Claim
18 words
The method according to claim 1, wherein the alkali metal base is a carbonate, borate, phosphate or silicate.
Claim 26
Dependent Claim
14 words
The method according to claim 1, wherein the base is a quaternary ammonium hydroxide.
Claim 27
Dependent Claim
19 words
The method according to claim 1, wherein the base has a pH greater than 11 at 0.1 normal concentration.
Claim 28
Dependent Claim
19 words
The method according to claim 1, wherein the total solids content is from 35 to about 60 weight percent.
Claim 29
Dependent Claim
36 words
The method according to claim 1, wherein the alkali metal compound being added in an amount from 2 to 6 weight percent on a dry basis based on the total solids calculated as sodium hydroxide equivalent.
Claim 30
Dependent Claim
18 words
The method according to claim 1, wherein the duration for mulling is from 5 minutes to 60 minutes.
Claim 31
Dependent Claim
18 words
The method according to claim 1, wherein the duration for mulling is from 15 minutes to 30 minutes.
Claim 32
Dependent Claim
19 words
The method according to claim 1, wherein the extrudate is dried at a temperature from 100° to 200° C.
Claim 33
Dependent Claim
23 words
The method according to claim 1, further comprising neutralizing the base used as an extrusion aid after drying and after calcining the extrudate.
Claim 34
Dependent Claim
22 words
The method according to claim 32, further comprising neutralizing using at least an equivalent of dilute nitric acid in ammonium nitrate solution.
Claim 35
Dependent Claim
28 words
The method according to claim 33, wherein an excess of dilute nitric acid in ammonium nitrate solution is used to neutralize the base used as an extrusion aid.
Claim 36
Dependent Claim
27 words
The method according to claim 1, further comprising neutralizing the base used as an extrusion aid after drying by circulating ammonium salt and adding acid during circulation.
Claim 37
Dependent Claim
13 words
The method according to claim 3, further comprising ion-exchanging the extruded dried zeolite.
Claim 38
Dependent Claim
16 words
The method according to claim 5, further comprising ion-exchanging the extruded dried and calcined silica-rich solid.
Claim 39
Dependent Claim
28 words
The method according to claim 36, further comprising calcining the ion-exchanged zeolite in inert gas at a temperature from 500° to 1000° F. for at least 1 hour.
Claim 40
Dependent Claim
34 words
The method according to claim 3, wherein the zeolite is ZSM-4, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, Zeolite Beta, zeolite X, zeolite Y, zeolite L, ferrierite, mordenite, dachiardite, clinoptolite, offretite, erionite, gmelinite, or chabazite.
Claim 41
Dependent Claim
12 words
The method according to claim 3, wherein the zeolite contains another metal.
Claim 42
Dependent Claim
26 words
The method of claim 1, further comprising treating the extrudate by steaming, acid extracting, calcining or a combination of those treatments to produce a stable extrudate.
Claim 43
Independent Claim
107 words
A method of extruding a mixture of silica and crystalline aluminosilicate solids which comprises mixing silica and ZSM-5 zeolite with water and sodium hydroxide followed by mulling and extruding, wherein the amount of water added being sufficient to have a total solids content of from 25 to 75 weight percent, the sodium hydroxide being added in an amount from 0.25 to 10 weight percent on a dried basis based on the total solids calculated as sodium hydroxide equivalent, and drying and calcining the extrudate whereby the extrudate has a crush strength of at least 4 pounds for a 1/8 inch length having a diameter of 1/16 inch.
Claim 44
Independent Claim
107 words
A method of extruding a mixture of silica and crystalline aluminosilicate solids which comprises mixing silica and ZSM-5 zeolite with water and sodium hydroxide followed by mulling and extruding, wherein the amount of water added being sufficient to have a total solids content of from 25 to 75 weight percent, the sodium hydroxide being added in an amount from 0.25 to 10 weight percent on a dried basis based on the total solids calculated as sodium hydroxide equivalent, and drying and calcining the extrudate whereby the extrudate has a crush strength of at least 4 pounds for a 1/8 inch length having a diameter of 1/16 inch.
Claim 45
Independent Claim
107 words
A method for extruding a mixture of silica and a crystalline aluminosilicate which comprises mixing silica and zeolite Y with water and sodium hydroxide followed by mulling and extruding, wherein the amount of water added being sufficient to have a total solids content of from 25 to 75 weight percent, the sodium hydroxide being added in an amount from 0.25 to 10 weight percent on a dried basis based on the total solids calculated as sodium hydroxide equivalent, and drying and calcining the extrudate whereby the extrudate has a crush strength of at least 4 pounds for a 1/8 inch length having a diameter of 1/16 inch.
Claim 46
Independent Claim
107 words
A method for extruding a mixture of silica and a crystalline aluminosilicate which comprises mixing silica and zeolite Y with water and sodium hydroxide followed by mulling and extruding, wherein the amount of water added being sufficient to have a total solids content of from 25 to 75 weight percent, the sodium hydroxide being added in an amount from 0.25 to 10 weight percent on a dried basis based on the total solids calculated as sodium hydroxide equivalent, and drying and calcining the extrudate whereby the extrudate has a crush strength of at least 4 pounds for a 1/8 inch length having a diameter of 1/16 inch.
Claim 47
Independent Claim
116 words
A method for increasing the silica-to-alumina ratio of a zeolite, comprising: mixing silica-rich solids containing zeolite with water and an alkali metal base or basic salt, the amount of water added being sufficient to have a total solids content of from 25 to 75 weight percent, the alkali metal compound being added in an amount from 0.25 to 10 weight percent on a dry basis based on the total solids calculated as sodium hydroxide equivalent; mulling and extruding the silica-rich mixture containing zeolite; drying the extrudate; ion-exchanging the extrudate with an ammonium salt to remove alkali metal; drying and calcining ammonium exchanged extrudate; dealuminizing the extrudate; and recovering a catalyst which can be substantially aluminum free.
Claim 48
Independent Claim
116 words
A method for increasing the silica-to-alumina ratio of a zeolite, comprising: mixing silica-rich solids containing zeolite with water and an alkali metal base or basic salt, the amount of water added being sufficient to have a total solids content of from 25 to 75 weight percent, the alkali metal compound being added in an amount from 0.25 to 10 weight percent on a dry basis based on the total solids calculated as sodium hydroxide equivalent; mulling and extruding the silica-rich mixture containing zeolite; drying the extrudate; ion-exchanging the extrudate with an ammonium salt to remove alkali metal; drying and calcining ammonium exchanged extrudate; dealuminizing the extrudate; and recovering a catalyst which can be substantially aluminum free.
Claim 49
Dependent Claim
12 words
The method according to claim 45, further comprising ion-exchanging the recovered catalyst.
Claim 50
Dependent Claim
20 words
The method according to claim 46, wherein ammonium, rare earth or other metals are used to ion-exchange the recovered catalyst.
Claim 51
Independent Claim
116 words
A method for increasing the silica-to-alumina ratio of zeolite Y, comprising: mixing a mixture of silica and zeolite Y with water and sodium hydroxide, the amount of water added being sufficient to have a total solids content of from 25 to 75 weight percent, the sodium hydroxide being added in an amount from 0.25 to 10 weight percent on a dry basis based on the total solids calculated as sodium hydroxide equivalent; mulling and extruding the mixture of silica and zeolite Y; drying the extrudate; ion-exchanging the extrudate with an ammonium salt to remove sodium; drying and calcining ammonium exchanged extrudate; dealuminizing the extrudate; and recovering a zeolite Y catalyst which can be substantially aluminum free.
Claim 52
Independent Claim
116 words
A method for increasing the silica-to-alumina ratio of zeolite Y, comprising: mixing a mixture of silica and zeolite Y with water and sodium hydroxide, the amount of water added being sufficient to have a total solids content of from 25 to 75 weight percent, the sodium hydroxide being added in an amount from 0.25 to 10 weight percent on a dry basis based on the total solids calculated as sodium hydroxide equivalent; mulling and extruding the mixture of silica and zeolite Y; drying the extrudate; ion-exchanging the extrudate with an ammonium salt to remove sodium; drying and calcining ammonium exchanged extrudate; dealuminizing the extrudate; and recovering a zeolite Y catalyst which can be substantially aluminum free.
Claim 53
Dependent Claim
10 words
A sorbent produced according to the method of claim 2.
Claim 54
Dependent Claim
10 words
A support produced according to the method of claim 2.
Claim 55
Dependent Claim
10 words
The support according to claim 50, containing a hydrogenation component.
Claim 56
Dependent Claim
19 words
The support according to claim 51, wherein the hydrogenation component being platinum, palladium, cobalt, molybdenum, iron or mixtures thereof.
Claim 57
Dependent Claim
15 words
The support according to claim 52, wherein the hydrogenation component being an oxide or salt.
Claim 58
Dependent Claim
25 words
The method according to claim 1, further comprising adding a catalytic material during mulling the mixture of silica-rich solids with water and alkali metal compound.
Claim 59
Dependent Claim
19 words
The method according to claim 54, wherein the catalytic material being platinum, palladium, cobalt, molybdenum, iron or mixtures thereof.
Claim 60
Dependent Claim
31 words
The method according to claim 1, wherein the dried and calcined extrudate has a crush strength from 5 to 24 pounds for a 1/8 inch length having a 1/16 inch diameter.
Claim 61
Dependent Claim
13 words
The method according to claim 1, wherein the silica-rich solids contain refractory oxides.
Claim 62
Dependent Claim
16 words
The method according to claim 57, wherein the refractory oxides being alumina, zirconia, magnesia or titania.
Claim 63
Dependent Claim
35 words
The method according to claim 1, wherein the extrudate has a porosity between 0.43 to about 1 cc/g and a pore size with greater than 70% of the pores being between 200 and 600 Angstroms.
Claim 64
Independent Claim
50 words
A method for extruding silica-rich solids, which comprises substituting an alkali metal for hydrogen in silanol groups on outside surfaces of the silica-rich solids, mulling and extruding the substituted silica-rich solids and drying the extrudate, whereby the dried extrudate has a crush strength superior to that of the prior art.
Claim 65
Independent Claim
50 words
A method for extruding silica-rich solids, which comprises substituting an alkali metal for hydrogen in silanol groups on outside surfaces of the silica-rich solids, mulling and extruding the substituted silica-rich solids and drying the extrudate, whereby the dried extrudate has a crush strength superior to that of the prior art.
Claim 66
Independent Claim
111 words
A method for extruding silica-rich solids, which comprises mixing the silica-rich solids with water in an alkali metal base or basic salt followed by mulling and extruding wherein the amount of water added being sufficient to have a solids content of from 25 to 75 wt. %, the alkali metal compound being added in an amount from 0.25 to 10 wt. % on a dry basis based on the total solids calculated as sodium hydroxide equivalent, drying the extrudate, and neutralizing the base used as an extrusion aid after drying and prior to calcining the extrudate, whereby the calcined extrudate has a crush strength superior to that of the prior art.
Claim 67
Independent Claim
111 words
A method for extruding silica-rich solids, which comprises mixing the silica-rich solids with water in an alkali metal base or basic salt followed by mulling and extruding wherein the amount of water added being sufficient to have a solids content of from 25 to 75 wt. %, the alkali metal compound being added in an amount from 0.25 to 10 wt. % on a dry basis based on the total solids calculated as sodium hydroxide equivalent, drying the extrudate, and neutralizing the base used as an extrusion aid after drying and prior to calcining the extrudate, whereby the calcined extrudate has a crush strength superior to that of the prior art.
Claim 68
Dependent Claim
26 words
The method according to claim 48, wherein the zeolite Y is dealuminized by alternately steaming and acid extracting a hydrogen form of the zeolite Y extrudate.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1989-04-14 | 1989-10-14 | 1990-04-15 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1993-04-14 | 1993-10-14 | 1994-04-15 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1997-04-14 | 1997-10-14 | 1998-04-15 | $7700.00 | Window Closed / Lapsed |