WO1992012792A1 - Alumina catalyst supports - Google Patents
Alumina catalyst supports Download PDFInfo
- Publication number
- WO1992012792A1 WO1992012792A1 PCT/GB1992/000122 GB9200122W WO9212792A1 WO 1992012792 A1 WO1992012792 A1 WO 1992012792A1 GB 9200122 W GB9200122 W GB 9200122W WO 9212792 A1 WO9212792 A1 WO 9212792A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aluminium
- oxyhydroxide
- catalyst
- aqueous medium
- paste
- Prior art date
- 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
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Classifications
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- 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
Definitions
- the present invention relates to modified alumina articles useful as catalyst supports, particularly for isomerisation of normal paraffins to produce high octane gasolines.
- Alumina in the form of shaped articles such as pellets produced by extrusion is useful as a catalyst support for a variety of purposes.
- Alumina pellets are used for example as supports for platinum catalysts used in the isomerisation of C 5 C 6 normal paraffins to produce branched paraffins as disclosed for example in GB 953 187.
- Shaped alumina catalyst supports may be prepared
- alumina supported catalysts are often described as alumina but in general, prior to calcination, they are not AI 2 O 3 but contain hydroxyl groups and are better described as aluminium oxyhydroxide.
- the process for producing a shaped aluminium oxyhydroxide article suitable for use as a catalyst support by mixing a powder of an aluminium oxyhydroxide and an aqueous medium to form a paste and then shaping the resulting paste to give a shaped article is characterised in that the aqueous medium contains a dissolved aluminium cationic compound.
- the aluminium oxyhydroxide powder may be any aluminium
- aluminium oxyhydroxide powder capable of peptisation to form an extrudable cough or paste capable of being formed into shapes by methods known in the prior art. It is preferably an aluminium oxyhydroxide with moderate to high surface acidity. Particularly preferred are high purity aluminium oxyhydroxides containing the minimum amounts of alkali metals, e.g. less than 0.08% wt and having surface areas and pore volumes in the range 1-1000m 2 /g and 0.01-3 cm 3 /g respectively.
- aluminium oxyhydroxides are produced as by-products of processes that use organoaiuminium compounds.
- Such aluminas are of very high purity containing high surface acidity and appreciable porosity.
- the cationic aluminium compound is of course a compound which is soluble in water. Where pellets of aluminium oxyhydroxide are used as catalyst supports it is frequently desirable to have relatively high surface acidities and in such cases the presence of metallic species which would reduce the surface activity of the final catalyst support is undesirable. Examples of such metallic species are K, Na, Ca and Mg . Examples of aluminium compounds which may be used are aluminium nitrate, aluminium sulphate and aluminium chloride.
- the concentration of the aluminium compound in the aqueous medium may for example be in the range 0.1 to 50% wt , based on weight of solution, preferably 5-25%, but the upper limit will of course be determined by the solubility of the aluminium compound.
- the relative amounts of aluminium oxyhydroxide and aqueous medium will be determined by the need to provide a paste of dough with appropriate viscosity for shaping, e.g. by extrusion.
- suitable proportions are 5.5 to 6.5 parts by weight of alumina to 4 parts by volume of aqueous medium (1.4:1 to 1.6:1) when parts by weight have the same relationship to parts by volume as grams to cubic centimetres.
- the mixing step may be carried out for sufficient time to give a uniform paste. Examples of suitable times are those in the range 5-45 minutes. The optimum time may depend on the type of mixer used.
- the catalyst supports of the present invention are particularly suitable for use in the production of catalysts for the
- temperatures in the range 66oC to 177oC temperatures in the range 66oC to 177oC, pressures of 1.55 MPa to 5.9 MPa, and space velocities in the range 0.2 to 5 and
- the isomerisation catalyst may be used for the
- Chloride may be introduced into the catalyst using, for example, carbon tetrachloride, chloroform, HCl, AICI 3 .
- the pellets were then dried and calcined in flowing air in a vessel whose temperature was increased from 50oC to 150°C at
- the alumina pellets (54.81 g) were impregnated with
- chloroplatinic acid (24.94% weight Pt, 0.7739 g) dissolved in distilled water (75 cm 3 ).
- the impregnated pellets were then evaporated to dryness in a rotary evaporator with the evaporator maintained in a bath at 80oC, with air blown into the rotating evaporator at 2000 cm 3 /min and an evaporation time of about 1 hcur.
- the impregnated pellets were then dried and calcined using the same temperature profile as before. They were then packed into a reactor and chlorided by saturating dry air at 20°C with CCl 4 vapour and passing that air/vapour mixture (400 cm 3 /minute, over the catalyst which was maintained at 250°C. This procedure was continued for 4.5 hours.
- the activity of the catalyst produced by chloriding the pellets was tested using a commercial C 5 /C 6 feedstock.
- the feedstock had the following composition:
- the catalyst was tested in a reactor with a capacity of 20 cm 3 and therefore the pellets were broken down to give particle. in the size range 1.4 to 0.5 mm to compensate for the small scale of the test.
- the test was carried out at a pressure of 35 bar (gauge) (3.6 MPa absolute), with a liquid hourly space velocity of 2, a reactor wall temperature of 145°C corresponding to a catalyst bed
- Aluminium oxyhydroxide pellets were prepared, converted to alumina, and tested as in Comparative Test A except that the quantity of aluminium oxyhydroxide powder was 1 kg and the quantity of aqueous medium was 650 cm 3 , and the aqueous medium was a 15% weight solution of Al (NO 3 ) 3 ⁇ 9H 2 O and the total mixing time in the Z-blade mixer was 7.5 minutes.
- Alumina pellets (62.56 g) were impregnated with chloroplatinic acid (0.8794 g, 24.94% weight Pt) dissolved in distilled water. The resulting Pt-containing pellets were then treated and tested as in Comparative test A.
- Aluminium oxyhydroxide pellets were produced, and converted to alumina, as in Comparative Test A. However instead of being impregnated with Pt they were impregnated with Pd. Alumina pellets (51.8 g) were impregnated with [(NH 3 ) 4 Pd] Cl 2 (0.4196 g) dissolved in distilled water (75 cm 3 ). The resulting product was then treated and tested as in Comparative Test A.
- Aluminium oxyhydroxide pellets were produced ana converted to alumina as in Example 1.
- the alumina pellets 50.74 g; were then impregnated with [(NH 3 ) 4 Pd] Cl 2 (0.4149 g) dissolved in distilled water (75 cm 3 ).
- the resulting product was then treated and tested as in Comparative Test A.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Shaped aluminium oxyhydroxide articles suitable for use as catalyst supports are made by mixing powder with an aqueous solution of a cationic alumina compound and shaping the resulting paste. The supports may be used for alkane isomerisation.
Description
ALUMINA CATALYST SUPPORTS
The present invention relates to modified alumina articles useful as catalyst supports, particularly for isomerisation of normal paraffins to produce high octane gasolines.
Alumina in the form of shaped articles such as pellets produced by extrusion is useful as a catalyst support for a variety of purposes. Alumina pellets are used for example as supports for platinum catalysts used in the isomerisation of C5C6 normal paraffins to produce branched paraffins as disclosed for example in GB 953 187.
Shaped alumina catalyst supports may be prepared
by mixing a finely divided alumina with water to form a paste and then extruding the resulting paste to give an extrudate which is then dried and then calcined by heating at elevated temperature. US 2 938 002 and GB 3 251 783 disclose such a procedure. The moisture required to give a paste is provided by the addition of deionised water.
W Stoeper and K K Unger, Preparation of Catalysts III, Elsevier Science Publishers B.V. (1983) pp.643-651 discuss the preparation of catalyst pellets from alumina powders by extruding aqueous pastes prepared from the powers. The use of dilute acids to convert alumina powers into extrudable pastes is discussed. The experiments used nitric acid as the dilute acid. It is stated that the different peptising effects of various organic and inorganic acids en microcrystalline boehmites based material depends on the strength of the acid and the tendency of the anion of the acid to form
complexes with aluminium. It is preferred to use strong acids whose anions are non-complexing or very weakly complexing with aluminium.
A Danner and K K Unger, Preparation of Catalysts IV, Elsevier Science Publishers B.V. (1987) pp.343-350 contains further
disclosures relating to the use of peptisation by nitric acid solution in the preparation of extrudable paste from alumina powders. It explains that there is an optimum concentration when using such peptising acids.
The starting materials used in the preparation of alumina supported catalysts are often described as alumina but in general, prior to calcination, they are not AI2O3 but contain hydroxyl groups and are better described as aluminium oxyhydroxide.
We have now found that a new method of peptising aluminium oxyhydroxide powders to convert them into extrudable paste.
According to the present invention the process for producing a shaped aluminium oxyhydroxide article suitable for use as a catalyst support by mixing a powder of an aluminium oxyhydroxide and an aqueous medium to form a paste and then shaping the resulting paste to give a shaped article is characterised in that the aqueous medium contains a dissolved aluminium cationic compound.
The aluminium oxyhydroxide powder may be any aluminium
oxyhycroxide powder capable of peptisation to form an extrudable cough or paste capable of being formed into shapes by methods known in the prior art. It is preferably an aluminium oxyhydroxide with moderate to high surface acidity. Particularly preferred are high purity aluminium oxyhydroxides containing the minimum amounts of alkali metals, e.g. less than 0.08% wt and having surface areas and pore volumes in the range 1-1000m2/g and 0.01-3 cm3/g respectively.
Particularly preferred aluminium oxyhydroxides are produced as by-products of processes that use organoaiuminium compounds. Such aluminas are of very high purity containing high surface acidity and appreciable porosity.
The cationic aluminium compound is of course a compound which is soluble in water. Where pellets of aluminium oxyhydroxide are used as catalyst supports it is frequently desirable to have
relatively high surface acidities and in such cases the presence of metallic species which would reduce the surface activity of the final catalyst support is undesirable. Examples of such metallic species are K, Na, Ca and Mg . Examples of aluminium compounds which may be used are aluminium nitrate, aluminium sulphate and aluminium chloride.
The concentration of the aluminium compound in the aqueous medium may for example be in the range 0.1 to 50% wt , based on weight of solution, preferably 5-25%, but the upper limit will of course be determined by the solubility of the aluminium compound.
The relative amounts of aluminium oxyhydroxide and aqueous medium will be determined by the need to provide a paste of dough with appropriate viscosity for shaping, e.g. by extrusion. Examples of suitable proportions are 5.5 to 6.5 parts by weight of alumina to 4 parts by volume of aqueous medium (1.4:1 to 1.6:1) when parts by weight have the same relationship to parts by volume as grams to cubic centimetres.
Examples of suitable proportions and preparation conditions are:
Aluminium oxyhydroxide (La Roche Versal 850) 604 g
Al(NO3)3·9H2O 15.8% wt solution in distilled water 380 cm3 Distilled water 50 cm3
Total mix time 23 mins
Aluminium oxyhydroxide (Condea Pural SB) 600 g
Al(NO3)3·9H2O 15.8% wt solution in distilled water 385 cm3 Distilled water 45 cm3
Total mix time 20 mins
The mixing together of the aluminium oxyhydroxide powder and the aqueous medium is conveniently carried out at ambient
temperature using any of the commercial mixers suitable for producing pastes or doughs for extrusion, e.g. Z-blade mixers. The mixing step may be carried out for sufficient time to give a uniform paste. Examples of suitable times are those in the range 5-45 minutes. The optimum time may depend on the type of mixer used.
The catalyst supports of the present invention are particularly suitable for use in the production of catalysts for the
isomerisation of normal alkanes over a catalyst comprising
(a) alumina support, (b) platinum, palladium or mixtures thereof and (c) chlorine. Such a process using Pt or Pd is disclosed for example in GB 899 378, GB 953 188 and GB 1 333 989. The production of catalysts for the isomerisation of n-alkanes is well known and therefore there is no need to describe the production or use of such catalysts in detail.
Thus the isomerisation reaction may be carried out at
temperatures in the range 66ºC to 177ºC, pressures of 1.55 MPa to 5.9 MPa, and space velocities in the range 0.2 to 5 and
hydrogen: hydrocarbon molar ratio of from 0.01 to 20:1 as disclosed in, for example, GB 953 188.
The isomerisation catalyst may be used for the
r.ydroisomerisation of waxes. Alternatively, the process may be applied in particular to C4 , C5 and C6 hydrocarbons, or to mixtures of two or more of such hydrocarbons. Chloride may be introduced into the catalyst using, for example, carbon tetrachloride, chloroform, HCl, AICI3.
The invention will now be described with reference to the following experiments in which experiments according to the
invention are identified by number and comparative tests, not according to the invention, are identified by letter.
Comparative Test A
The starting material was a aluminium oxyhydroxide powder having the following characteristics
Chemical analysis % wt
AI2O3 75
Carbon 0.3
SiO2 0.01
Fe2O3 0.01
Na2O 0.002
Crystal structure Boehmite (alpha alumina
monohydrate)
Surface area m2/g after activation at 250 m2/g
550ºC for 3 hours
Pore volume calculated by the method 0.58 cm3/g
of Dollimore and Heal
(specifications from the manufacturers)
This material is commercially available under the trade name
"Pural SB". The aluminium oxyhydroxide powder (2 kg) was mixed with a 5% volume/volume aqueous solution of nitric acid (1250 cm3) in a Z-blade mixer. The total mixing time was 10 minutes. The dough was then extruded through a die having a diameter of 0.79 inches
(2 mm) to produce cylindrical pellets with a length of 3-4
mm. The pellets were then dried and calcined in flowing air in a vessel whose temperature was increased from 50ºC to 150°C at
100'C/hour and held at 150ºC for 2 hours. It was then heated from 150ºC to 350°C at 100ºC/hour and held at 350ºC for 2 hours and then from 250°C to 550ºC at 100'C/hour and held for 4 hours. The pellets were then allowed to cool in flowing air. As a result of the calcination step the original aluminium oxyhydroxide suffers loss of hydroxyl groups and the calcined product will be referred to as alumina.
The alumina pellets (54.81 g) were impregnated with
chloroplatinic acid (24.94% weight Pt, 0.7739 g) dissolved in distilled water (75 cm3). The impregnated pellets were then evaporated to dryness in a rotary evaporator with the evaporator maintained in a bath at 80ºC, with air blown into the rotating evaporator at 2000 cm3/min and an evaporation time of about 1 hcur.
The impregnated pellets were then dried and calcined using the same temperature profile as before. They were then packed into a reactor and chlorided by saturating dry air at 20°C with CCl4 vapour and passing that air/vapour mixture (400 cm3/minute, over the catalyst which was maintained at 250°C. This procedure was continued for 4.5 hours.
The activity of the catalyst produced by chloriding the pellets was tested using a commercial C5/C6 feedstock.
The feedstock had the following composition:
The catalyst was tested in a reactor with a capacity of 20 cm3 and therefore the pellets were broken down to give particle. in the size range 1.4 to 0.5 mm to compensate for the small scale of the test. The test was carried out at a pressure of 35 bar (gauge) (3.6 MPa absolute), with a liquid hourly space velocity of 2, a reactor wall temperature of 145°C corresponding to a catalyst bed
temperature of about 135°C. Hydrogen was fed with the hydrocarbon feed to give a hydrogen/hydrocarbon molar ratio of 2.3:1.
The proαuct leaving the reactor was analysed and the
conversions of C5 and C6 were determined. The results are shown in Table 2.
Example 1
Aluminium oxyhydroxide pellets were prepared, converted to alumina, and tested as in Comparative Test A except that the quantity of aluminium oxyhydroxide powder was 1 kg and the quantity of aqueous medium was 650 cm3, and the aqueous medium was a 15% weight solution of Al (NO3)3·9H2O and the total mixing time in the Z-blade mixer was 7.5 minutes.
Alumina pellets (62.56 g) were impregnated with chloroplatinic acid (0.8794 g, 24.94% weight Pt) dissolved in distilled water. The resulting Pt-containing pellets were then treated and tested as in Comparative test A.
The results are given in Table 2.
Comparative Test B
Aluminium oxyhydroxide pellets were produced, and converted to alumina, as in Comparative Test A. However instead of being impregnated with Pt they were impregnated with Pd. Alumina pellets (51.8 g) were impregnated with [(NH3)4Pd] Cl2 (0.4196 g) dissolved in distilled water (75 cm3). The resulting product was then treated and tested as in Comparative Test A.
The results are given in Table 2.
Example 2
Aluminium oxyhydroxide pellets were produced ana converted to alumina as in Example 1. The alumina pellets (50.74 g; were then impregnated with [(NH3)4Pd] Cl2 (0.4149 g) dissolved in distilled water (75 cm3). The resulting product was then treated and tested as in Comparative Test A.
The % C5 Conversion is given by
% wt i-C5 × 100
% wt i-C5 + wt n-C5 The % C6 conversion is given by
% wt 2,2-DMB × 100
% wt 2,2-DMB + % wt 2,3-DMB + % 2-MP + % wt 3-MP + % wt n-C6
(where i-C5 is isopentane, n-C5 is n-pentane, DMB is dimethyl butane, MP is methyl pentane, n-C6 is n-hexane.)
Claims
1. The process for producing a shaped aluminium oxyhydroxide article suitable for use as a catalyst support by mixing a powder of an aluminium oxyhydroxide and an aqueous medium to form a paste and then shaping the resulting paste to give a shaped article is characterised in that the aqueous medium contains a dissolved aluminium cationic compound.
2. The process according to Claim 1 wherein the aluminium oxyhydroxide is a high purity aluminium oxyhydroxide having a surface area in the range 1 to 1000 m2/g and a pore volume in the range 0.01 to 3 cm3/g, respectively.
3. The process according to either one of Claims 1 or 2 wherein the aluminium oxyhydroxide is produced as a by-product of a process using organo aluminium compounds.
4. The process according to any one of the preceding claims wherein the aluminium compound is aluminium nitrate, aluminium sulphate, or aluminium chloride.
5. The process according to any one of the preceding claims wnerein the ratio of the weight of aluminium oxyhydroxide (expressed in grams) to the volume of aqueous medium (.expressed in cm3) is in the range 1.4:1 to 1.6:1.
6. The catalyst for the isomerisation of an n-aikane, which catalyst comprises an alumina support, platinium, palladium or mixtures thereof, and chlorine characterised in that the alumina support is produced by a process which includes the step of mixing the powder of an aluminium oxyhydroxide and an aqueous medium containing a dissolved aluminium cationic compound in order to form a paste, followed by shaping the resulting paste to give a shaped article.
7. A process according to Claim 7 wherein catalyst contains palladium.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9101571.9 | 1991-01-24 | ||
| GB919101571A GB9101571D0 (en) | 1991-01-24 | 1991-01-24 | Modified alumina supports |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1992012792A1 true WO1992012792A1 (en) | 1992-08-06 |
Family
ID=10688952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB1992/000122 Ceased WO1992012792A1 (en) | 1991-01-24 | 1992-01-21 | Alumina catalyst supports |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU1173492A (en) |
| GB (1) | GB9101571D0 (en) |
| WO (1) | WO1992012792A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4113789A (en) * | 1977-03-03 | 1978-09-12 | Texaco Inc. | Hydroisomerization of normal paraffin with a catalyst of noble metal, alumina support and chlorine |
| US4275052A (en) * | 1980-05-02 | 1981-06-23 | Uop Inc. | Process for preparing high surface area aluminas |
| EP0038705A2 (en) * | 1980-04-21 | 1981-10-28 | Sumitomo Aluminium Smelting Company Limited | Process for the production of a low density activated alumina formed product |
| US4705767A (en) * | 1986-12-15 | 1987-11-10 | W. R. Grace & Co. | Sulfactants in acid-peptized catalyst compositions |
-
1991
- 1991-01-24 GB GB919101571A patent/GB9101571D0/en active Pending
-
1992
- 1992-01-21 AU AU11734/92A patent/AU1173492A/en not_active Abandoned
- 1992-01-21 WO PCT/GB1992/000122 patent/WO1992012792A1/en not_active Ceased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4113789A (en) * | 1977-03-03 | 1978-09-12 | Texaco Inc. | Hydroisomerization of normal paraffin with a catalyst of noble metal, alumina support and chlorine |
| EP0038705A2 (en) * | 1980-04-21 | 1981-10-28 | Sumitomo Aluminium Smelting Company Limited | Process for the production of a low density activated alumina formed product |
| US4275052A (en) * | 1980-05-02 | 1981-06-23 | Uop Inc. | Process for preparing high surface area aluminas |
| US4705767A (en) * | 1986-12-15 | 1987-11-10 | W. R. Grace & Co. | Sulfactants in acid-peptized catalyst compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9101571D0 (en) | 1991-03-06 |
| AU1173492A (en) | 1992-08-27 |
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