AU602258B2 – Silica-alumina extrudates
– Google Patents
AU602258B2 – Silica-alumina extrudates
– Google Patents
Silica-alumina extrudates
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Publication number
AU602258B2
AU602258B2
AU23931/88A
AU2393188A
AU602258B2
AU 602258 B2
AU602258 B2
AU 602258B2
AU 23931/88 A
AU23931/88 A
AU 23931/88A
AU 2393188 A
AU2393188 A
AU 2393188A
AU 602258 B2
AU602258 B2
AU 602258B2
Authority
AU
Australia
Prior art keywords
silica
alumina
weight
mixture
solids content
Prior art date
1987-10-19
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
AU23931/88A
Other versions
AU2393188A
(en
Inventor
Jacobus Theodorus Daamen
Tom Huizinga
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1987-10-19
Filing date
1988-10-17
Publication date
1990-10-04
1988-10-17
Application filed by Shell Internationale Research Maatschappij BV
filed
Critical
Shell Internationale Research Maatschappij BV
1989-04-20
Publication of AU2393188A
publication
Critical
patent/AU2393188A/en
1990-10-04
Application granted
granted
Critical
1990-10-04
Publication of AU602258B2
publication
Critical
patent/AU602258B2/en
2008-10-17
Anticipated expiration
legal-status
Critical
Status
Ceased
legal-status
Critical
Current
Links
Espacenet
Global Dossier
Discuss
Classifications
B—PERFORMING OPERATIONS; TRANSPORTING
B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
B—PERFORMING OPERATIONS; TRANSPORTING
B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
B01J21/12—Silica and alumina
Abstract
The invention relates to a process for the preparation of a shapable dough which comprises mixing and kneading a particulate silica-alumina with water and with an alkanolamine or ammonia to obtain a mixture having a total solids content of from 25 to 60% by weight, the alkanolamine or ammonia being present in an amount of from 0.5 to 20% by weight on the total solids content of the mixture, to a shapable dough obtained by this process, to the preparation of silica-alumina extrudates therefrom and to their use as catalyst carriers in hydrocarbon conversion or hydrocarbon synthesis reactions.
Description
ji :c\ 602258 S F Ref: 73717 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE: Class Int Class Complete Specification Lodged: Accepted: Published: Priority: Related Art: Name and Address of Applicant: Address for Service: Shell Internationale Research Maatschappij B.V.
Carel van Bylandtlaan 2596 HR The Hague THE NETHERLANDS Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia I I t cc t C C C C C CC
C
C. f t Complete Specification for the invention entitled: Silica-alumina Extrudates The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/3 k t :2 a ~~a*U–U-rrrU~r;F4ilr T 226 SILICA-ALUMINA EXTRUDATES The invention relates to the preparation of silica-alumina extrudates, to the preparation of a shapable dough for silica-alumina extrudates, to a shapable dough for silica-alumina extrudates and to the preparation of calcined silica-alumina extrudates and to their use.
In European patent application (publication) 167 324 is disclosed a method for the preparation of a silica extrudate whereby a particulate silica is mixed with water and an alkali metal compound to prepare a mixture which is extruded. However, the use of an alkali metal makes it necessary that the extruded silica must be soaked in a solution of ammonium nitrate and nitric acid to remove the alkali metal. The same applies to silicas containing another refractory oxide, such as alumina, according to the above-mentioned European patent application (publication) 167,324.
Applicant has found that this purification process i may be obviated by using an alkanolamine or ammonia in the preparation of a dough from which silica-alumina i extrudates can be obtained.
The invention therefore relates to a process for i the preparation of a shapable dough which comprises mixing and kneading a particulate silica-alumina with water and with an alkanolamine or ammonia to obtain a mixture having a total solids content of from 25 to by weight, the alkanolamine or ammonia being present in an amount of from 0.5 to 20% by weight on the total solids content of the mixture.
The invention further relates to a process for the preparation of silica-alumina extrudates which 2 comprises mixing and kneading a particulate silicaalumina with water and with an alkanolamine or ammonia to obtain a mixture having a total solids content of from 25 to 60% by weight, the alkanolamine or ammonia being present in an amount of from 0.5 to 20% by weight on the total solids content of the mixture and extruding the mixture.
The invention further relates to a process for manufacturing calcined silica-alumina extrudates which comprises extruding a shapable dough into silicaq alumina extrudates and drying and calcining the silica-alumina extrudates to a final temperature of 0 0 between 300 C and 1000 C, and to calcined silicaalumina extrudates obtained by this process.
The silica-alumina to be used in the process according to our invention is silica-alumina obtained 0 by reacting a silicate, preferably sodium- or potassium silicate, with an acid in the presence of an aluminium compound. Preferred is the washed silica-alumina filter cake.
SWhen silica-alumina gel is gradually heated to a higher temperature it loses water. Heating during longer times above 100 C results in that the water Scontent decreases to about 5% by weight. The water content of the silica-alumina is determined by weight Sloss on ignition (LOI). A sample is weighed and then placed in a muffle furnace where it is heated at 1000 0 i C for 2 hours. After heating the sample is again weighed. The difference in weights represents the LOI or the amount of water present in the silica-alumina.
When silica-alumina has been calcined, at e.g. 500 C, it seems less suitable for use in the extrusion process. However silica-alumina gels which have been spray dried are very suitable.
i 3 The total solids content of the mixture of silicaalumina, ammonia or alkanolamine and water ranges from to 60% by weight, preferably from 30 to 45% by weight and more preferably from 35 to 40% by weight, in order to obtain an extrudable mixture.
The amount of alkanolamine or ammonia ranges from to 20% by weight, preferably from 2 to 15% by weight, more preferably from 3 to 10% by weight alculated on the total solids content.
i 10 To improve the flux properties in the extruder the mixture may also comprise a polyelectrolyte, such as Nalco 7879 (obtained from Nalco). The mixture (with or without polyelectrolyte) can readily be extruded e.g.
over the metal die-plate of the Bonnot-extruder.
Cylindrical extrudates can be prepared, but other forms may be prepared as well, such as mentioned in US patent specification 4,028,227. It is possible to prepare silica-alumina with a surface area of more than 350 m 2/g.
m S/g.
The alkanolamines to be used in the process according to the invention may be mono-, di- or trialkanolamines. Preferred are monoalkanolamines, such as those containing 2 to 10 carbon atoms, e.g. ethanol- Samine, propanolamine, hexanolamine, nonanolamine and decanolamine. Other examples are diethanolamine and triethanolamine.
It is possible prior to extrusion to admix I titanium dioxide or zirconium dioxide to the composition. This is advantageous when the silicaalumina is used as carrier and the titanium and zirconium are the effective catalyst ingredients.
The extruded silica-aluminas may be suitably used, for example, as carriers for catalysts, which are normally used in hydrocarbon conversion, like hydrodemetallization of heavy hydrocarbon oils, in _1 i- 4 hydrocarbon synthesis reactions, in t..e epoxidation of olefinically unsaturated compounds w-in organic hydroperoxides, in the hydrations of olefinically unsaturated compounds to produce the corresponding alkanols and in the purification of exhaust gases.
EXAMPLE
A mixture was prepared having the following composition: silica-alumina (ex Crossfield, 25 %w A1 2 0 3 1040 g (solids 800 g) ethanolamine 40 g water (demineralized) 920 g total 2000 g (LOI is The mixture was prepared by adding the ethanolamine and water to the silica-alumina and the mixture was kneaded for 45 min. The total kneaded mixture was extruded. The obtained extrudates (diameter 1.5 mm) were dried at 120 C for 2 h, broken to pieces of about 4 to 5 mm and calcined at 500 C for 2 h. The silica-alumina extrudate had the following properties: BET surface area 379 m2/g pore volume 0.91 ml/g (mercury intrusion) bulk crushing strength 0.62 MPa.
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Claims (11)
1. A process for the preparation of a shapable dough which comprises mixing and kneading a particulate silica-alumina with water and with an alkanolamine or ammonia to obtain a mixture having a total solids content of from 25 to 60% by weight, the alkanolamine or ammonia being present in an amount of from 0.5 to by weight on the total solids content of the mixture.
2. A process according to claim 1 wherein the silica-alumina is obtained by reacting a silicate with acid in the presence of an aluminium compound.
3. A process according to claim 2 wherein r silica-alumina filter cake is used.
4. A process according to any one of the claims 1-3, wherein the total solids content is from 30 to 45% by weight, preferably 35 to 40% by weight. A process according to any one of the claims 1-4, wherein the alkanolamine or ammonia is present in an amount of from 3 to 10% by weight on the total solids content.
6. A process according to any one of the claims wherein a polyelectrolyte is admixed into the mixture.
7. A process according to any one of the claims 1-6, wherein titanium dioxide or zirconium dioxide is 25 admixed.
8. A process for the preparation of silica-alumina extrudates from a shapable dough according to claim 1, which comprises mixing and kneading a particulate silica-alumina with water and with an alkanolamine or ammonia to obtain a mixture having a total solids content of from 25 to 60% by weight, the alkanolamine 6 or ammonia being present in an amount of from 0.5 to by weight on the total solids content of the mixture and extruding the mixture.
9. A process for manufacturing calcined silica-alumina extrudates which comprises drying and calcining the silica-alumina extrudates prepared by the process according to claim 8, to a final temperature of between 300 °C and 1000 0 C. Use of silica-alumina extrudates prepared by a process according to claim 9 as catalyst carriers in i hydrocarbon conversion or hydrocarbon synthesis reactions.
11. A process for the preparation of a shapable dough substantially as hereinbefore described with reference to any one of the Examples.
12. A process for the preparation of silica-alumina extrudates from a shapable dough substantially as hereinbefore described with reference to any one of the Examples.
13. The product of the process of any one of claims 1 to 9. DATED this TNENTY-NINTH day of SEPTEMBER 1988 Shell Internationale Research Maatschappij B.V. Patent Attorneys for the Applicant SPRUSON FERGUSON T4/T226
AU23931/88A
1987-10-19
1988-10-17
Silica-alumina extrudates
Ceased
AU602258B2
(en)
Applications Claiming Priority (2)
Application Number
Priority Date
Filing Date
Title
GB878724436A
GB8724436D0
(en)
1987-10-19
1987-10-19
Silica-alumina extrudates
GB8724436
1987-10-19
Publications (2)
Publication Number
Publication Date
AU2393188A
AU2393188A
(en)
1989-04-20
AU602258B2
true
AU602258B2
(en)
1990-10-04
Family
ID=10625528
Family Applications (1)
Application Number
Title
Priority Date
Filing Date
AU23931/88A
Ceased
AU602258B2
(en)
1987-10-19
1988-10-17
Silica-alumina extrudates
Country Status (10)
Country
Link
US
(1)
US4888319A
(en)
EP
(1)
EP0313163B1
(en)
JP
(1)
JP2620127B2
(en)
AT
(1)
ATE64111T1
(en)
AU
(1)
AU602258B2
(en)
CA
(1)
CA1321215C
(en)
DE
(1)
DE3863160D1
(en)
ES
(1)
ES2022605B3
(en)
GB
(1)
GB8724436D0
(en)
ZA
(1)
ZA887717B
(en)
Families Citing this family (6)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
US5074990A
(en)
*
1987-10-30
1991-12-24
Exxon Research And Engineering Company
Fluid catalytic cracking using catalysts containing an alumina-on-silica component
FR2670687A1
(en)
*
1990-12-21
1992-06-26
Shell Int Research
PROCESS FOR THE EXTRUSION OF CRYSTALLINE ALUMINOSILICATES.
MY109378A
(en)
*
1992-08-18
1997-01-31
Shell Int Research
Process for the preparation of a catalyst for a catalyst precursor
MY131860A
(en)
*
2000-06-21
2007-09-28
Shell Int Research
Process for preparation of catalyst and use there of
US7825204B2
(en)
2006-12-19
2010-11-02
Lyondell Chemical Technology, L.P.
Inorganic oxide extrudates
US7563740B2
(en)
*
2006-12-19
2009-07-21
Lyondell Chemical Technology, L.P.
Direct epoxidation process
Citations (2)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
US4264474A
(en)
*
1978-08-21
1981-04-28
Filtrol Corporation
Ammoniated silica-alumina gel and catalyst containing the same and processes for producing same
US4542118A
(en)
*
1984-02-02
1985-09-17
W. R. Grace & Co.
Catalyst manufacture
Family Cites Families (12)
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Publication number
Priority date
Publication date
Assignee
Title
US2348072A
(en)
*
1943-03-31
1944-05-02
Universal Oil Prod Co
Manufacture of catalysts
US2480669A
(en)
*
1946-04-24
1949-08-30
Socony Vacuum Oil Co Inc
Process of preparing extruded gels
US3519574A
(en)
*
1964-02-14
1970-07-07
American Cyanamid Co
Process for manufacture of catalyst material and catalyst material produced thereby
US3390100A
(en)
*
1964-02-14
1968-06-25
American Cyanamid Co
Process for the preparation of extrudates from hydrogels
US3346509A
(en)
*
1964-06-12
1967-10-10
Gulf Research Development Co
Co-precipitated silica-alumina catalyst process and composition
US3442821A
(en)
*
1966-09-29
1969-05-06
Universal Oil Prod Co
Manufacture of spheroidal silica-alumina particles
FR2154905A5
(en)
*
1971-09-29
1973-05-18
Engelhard Min & Chem
Silica-alumina catalysts – contg relatively high concns of alkali metals
US4039474A
(en)
*
1975-10-20
1977-08-02
Nalco Chemical Company
Silica-alumina catalysts
US4174301A
(en)
*
1977-08-31
1979-11-13
Nalco Chemical Company
Polycarboxylic acids as extrusion aids for silica-aluminas
US4256682A
(en)
*
1980-03-05
1981-03-17
W. R. Grace & Co.
Method of preparing silica gel pellets
DE3132674C2
(en)
*
1981-08-19
1983-12-08
Degussa Ag, 6000 Frankfurt
Process for the production of compacts
US4582815A
(en)
*
1984-07-06
1986-04-15
Mobil Oil Corporation
Extrusion of silica-rich solids
1987
1987-10-19
GB
GB878724436A
patent/GB8724436D0/en
active
Pending
1988
1988-10-04
CA
CA000579205A
patent/CA1321215C/en
not_active
Expired – Fee Related
1988-10-11
US
US07/256,012
patent/US4888319A/en
not_active
Expired – Lifetime
1988-10-17
ZA
ZA887717A
patent/ZA887717B/en
unknown
1988-10-17
AU
AU23931/88A
patent/AU602258B2/en
not_active
Ceased
1988-10-17
JP
JP63259623A
patent/JP2620127B2/en
not_active
Expired – Lifetime
1988-10-18
DE
DE8888202328T
patent/DE3863160D1/en
not_active
Expired – Fee Related
1988-10-18
ES
ES88202328T
patent/ES2022605B3/en
not_active
Expired – Lifetime
1988-10-18
EP
EP88202328A
patent/EP0313163B1/en
not_active
Expired – Lifetime
1988-10-18
AT
AT88202328T
patent/ATE64111T1/en
not_active
IP Right Cessation
Patent Citations (2)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
US4264474A
(en)
*
1978-08-21
1981-04-28
Filtrol Corporation
Ammoniated silica-alumina gel and catalyst containing the same and processes for producing same
US4542118A
(en)
*
1984-02-02
1985-09-17
W. R. Grace & Co.
Catalyst manufacture
Also Published As
Publication number
Publication date
GB8724436D0
(en)
1987-11-25
ES2022605B3
(en)
1991-12-01
ATE64111T1
(en)
1991-06-15
AU2393188A
(en)
1989-04-20
EP0313163B1
(en)
1991-06-05
US4888319A
(en)
1989-12-19
JP2620127B2
(en)
1997-06-11
CA1321215C
(en)
1993-08-10
DE3863160D1
(en)
1991-07-11
EP0313163A1
(en)
1989-04-26
JPH01145369A
(en)
1989-06-07
ZA887717B
(en)
1989-06-28
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Legal Events
Date
Code
Title
Description
2003-05-22
MK14
Patent ceased section 143(a) (annual fees not paid) or expired
