Catalyst and method of manufacture

Abstract

A method for making a solid material which is useful as a heterogeneous catalyst including the steps of: forming at least one copper oxide suspension comprising solid particles of copper oxide in a liquid; forming at least one carrier suspension comprising solid particles of a carrier material in a liquid; combining the copper oxide suspension and the carrier suspension; subjecting the combined suspensions to mechanical energy; separating the suspension liquid from the solid particles in the combined suspension; and subjecting the solid material to a thermal decomposition step. A catalyst made by the method has a BET surface area greater than 150 m.sup.2/g, a particle size distribution in which D50 is in the range from 25-35 m, and wherein the D50 after 60 minutes ultrasound treatment is at least 30% of the original value.

Claims

1. A solid particulate catalyst comprising copper oxide and a solid carrier material, wherein said solid particulate catalyst is in the form of a powder having a BET surface area greater than 150 m.sup.2/g, a particle size distribution in which D50 is in the range from 25-35 m, and wherein the D50 after 60 minutes ultrasound treatment is at least 30% of the original value.

2. A solid particulate catalyst according to claim 1 which is obtainable by the preparation method of comprising the steps of: (a) forming at least one copper oxide suspension comprising solid particles of copper oxide in a liquid; (b) forming at least one carrier suspension comprising solid particles of a carrier material in a liquid; (c) combining the copper oxide suspension and the carrier suspension; d) subjecting the combined suspensions to mechanical energy; (e) separating the suspension liquid from the solid particles in the combined suspension; and (f) subjecting the separated solid particles to a thermal decomposition step.

3. A solid particulate catalyst according to any claim 1, wherein the carrier material comprises a metal oxide.

4. A solid particulate catalyst according to claim 3, wherein the carrier material comprises silica-alumina, silica, alumina, zirconia or titania.

5. A method for making the solid particulate catalyst of claim 1 which is useful as a heterogeneous catalyst comprising the steps of: (a) forming at least one copper oxide suspension comprising solid particles of copper oxide in a liquid; (b) forming at least one carrier suspension comprising solid particles of a carrier material in a liquid; (c) combining the copper oxide suspension and the carrier suspension; (d) subjecting the combined suspensions to mechanical energy; (e) separating the suspension liquid from the solid particles in the combined suspension; and (f) subjecting the separated solid particles to a thermal decomposition step.

6. A method according to claim 5 consisting essentially of steps (a)-(f).

7. A method according to claim 5, wherein the material comprises from 5% to 90% by weight of copper oxide.

8. A method according to claim 5, wherein step (d) comprises subjecting the combined suspensions to a milling or grinding process.

9. A method according to claim 5, wherein in step (d) the mechanical energy applied to the combined suspensions is greater than 500 W/liter.

10. A method according to claim 5, wherein the carrier material comprises a metal oxide.

11. A method according to claim 10, wherein the carrier material comprises silica-alumina, silica, alumina, zirconia or titania.

12. A process for carrying out a chemical reaction selected from the type of reaction including hydrogenation, hydrogenolysis, amination and dehydrogenation, comprising adding a solid particulate catalyst according to claim 1 to a reaction mixture.

13. The process according to claim 12, wherein the reaction is for hydrogenation of carbonyl groups.

14. The process according to claim 13, wherein the reaction is for the production of a fatty alcohol.

Description

EXAMPLE 1

(1) A catalyst according to the invention was prepared according to the following method. 3 parts of a suspension containing 20% by weight of copper oxide powder (D50=45 m) in water was combined with 2 parts of a suspension containing 20% by weight of silica-alumina powder (Siral-10, 90 wt % alumina, 10 wt % silica, Sasol Germany, D50=30 m) in water.

(2) The combined suspensions were milled in a stirrer bead mill (Fryma MS 32 using 1 mm zirconium silicate beads filling 75% of the volume) operating at 3000 rpm (27 kW input) and a throughput of 150 liters/hour over 8.5 hours. The milled suspension was then spray-dried to <2% moisture content in a rotary disc dryer operating at an inlet temperature of 300 C. and outlet temperature 90 C. The resulting solids were calcined in air at 320 C. to yield a material with a loss on ignition (800 C., 2 h) of <15%. The particle size distribution, measured using a Malvern Mastersizer laser diffraction apparatus, is shown in Table 1. The surface area was measured using the BET method of nitrogen adsorption at 77K.

COMPARATIVE EXAMPLE 2

(3) 3 Parts of a suspension containing 20% by weight of copper oxide powder (D50=45 m) in water was combined with 2 parts of a suspension containing 20% by weight of silica alumina powder (Siral-10, 90 wt % alumina, 10 wt % silica, Sasol Germany, D50=30 m) in water. The combined suspensions were milled in a stirrer bead mill (Fryma MS 32 using 1 mm zirconium silicate beads filling 75% of the volume) operating at 3000 rpm (27 kW input) and a throughput of 150 liters/hour over 8.5 hours. The milled suspension was then spray-dried in a rotary disc dryer operating at an inlet temperature of 300 C. and outlet temperature 90 C. to <2% moisture content. 10% demineralised water was added to the solids, and the solids were then further dried in a vacuum extruder (Hndle, Type XC) at 10 to 20 mbar and a temperature range of 110 to 130 C. and formed into a granulate with a diameter of 2 mm. The resulting solids were calcined in air at 320 C. to yield a material with a loss on ignition (800 C., 2 h) of <15%and subsequently milled using a mortar grinder.

COMPARATIVE EXAMPLE 3

(4) 3 Parts of a suspension containing 20% by weight of copper oxide powder (D50=45 m) in water was combined with 2 parts of a suspension containing 20% by weight of silica alumina powder (Siral-10, 90 wt % alumina, 10 wt % silica, Sasol Germany, D50=30 m) in water. The combined suspensions were milled in a stirrer bead mill (Fryma MS 32 using 1 mm zirconium silicate beads filling 75% of the volume) operating at 3000 rpm (27 kW input) and a throughput of 150 liters/hour over 8.5 hours. The milled suspension was then spray-dried in a rotary disc dryer operating at an inlet temperature of 300 C. and outlet temperature 90 C. to <2% moisture content. 10% demineralised water was added to the solids, and the solids were then further dried in a vacuum extruder (Hndle, Type XC) at 10 to 20 mbar and a temperature range of 110 to 130 C. and formed into a granulate with a diameter of 2 mm and subsequently milled using a mortar grinder.

COMPARATIVE EXAMPLE 4

(5) 5 Parts of a suspension containing 20% by weight of copper hydroxycarbonate powder (D50=50 m, TIB Chemicals, ca 47% copper) in water was combined with 2 parts of a suspension containing 20% by weight of silica alumina powder (Siral-10, 90 wt % alumina, 10 wt % silica, Sasol Germany, D50=30 m) in water. The combined suspensions were milled in a stirrer bead mill (Fryma MS 32 using 1 mm zirconium silicate beads filling 75% of the volume) operating at 3000 rpm (27 kW input) and a throughput of 150 liters/hour over 8.5 hours. The milled suspension was then spray-dried in a rotary disc dryer operating at an inlet temperature of 300 C. and outlet temperature 90 C. to <2% moisture content. The resulting solids were calcined in air at 320 C. to yield a material with a loss on ignition (800 C., 2 h) of <15%.

EXAMPLE 5

Activity Test

(6) 7 g of each of the catalysts made in Examples 1-4 was tested in the hydrogenation of 300g fatty C12-C18 methyl ester to alcohol in a 1 liter autoclave at 280 C. at 100 bar hydrogen pressure. The conversion after a reaction time of 30 minutes is shown in Table 1. A commercially available copper chromite catalyst was also tested as an additional comparison.

EXAMPLE 6

Attrition

(7) A sample of each of the catalysts was tested using the attrition test described above. The particle size distribution (D50) after 60 minutes of this treatment (or, where shown, after only 30 minutes) is shown in Table 1 as D50A. The attrition % is calculated as 100((D50D50A)/D50).

(8) TABLE-US-00001 TABLE 1 Com- Com- Com- Com- parative Example parative parative parative copper 1 Example 2 Example 3 Example 4 chromite BET SA 168 116.6 152 123.0 40 (m2/g) D50 (m) 30 44.6 30 38.2 25 D90 (m) 57.5 75.5 61.9 62.6 31.3 D10 (m) 21.2 11.9 20.3 7.2 2.6 (D90 D10)/ 1.21 1.43 1.39 1.45 1.15 D50 D50A (m) 12.1 15 5.6 After After after 60 min 30 min 30 min 3 3 Attrition % 60 66 81 92 88 Activity 70 67.2 68.7 63.0 70 (% conversion)