Supported noble metal-comprising catalyst for oxidative dehydrogenation or epoxidation

Patent metadata

Field	Value
Publication number	US-9346035-B2
Application number	US-201314418487-A
Country	US
Kind code	B2
Filing date	Jul 31, 2013
Priority date	Aug 1, 2012
Publication date	May 24, 2016
Grant date	May 24, 2016

Abstract

Supported noble metal-comprising catalysts which can be obtained by a1) application of a noble metal compound, optionally in admixture with additives acting as promoters, to a support material, then drying, and a2) application of a reducing agent to a support material, then drying, wherein steps a1) and a2) are repeated simultaneously or in alternating turns, or wherein either of the compounds is applied entirely and then the other one is applied entirely, b) optionally afterwards drying of the resulting product, and c) subsequent calcination, its use, especially for oxidative dehydrogenation and a process for producing it.

First claim

The invention claimed is:

1. A process comprising utilizing a supported noble metal-comprising catalyst prepared by
I-a1) application of a noble metal compound, optionally in admixture with additives acting as promoters, to a support material, then drying at from 60 to 200° C. for 10 to 180 seconds,
and
I-a2) application of a reducing agent to a support material, then drying at from 60 to 200° C. for 10 to 180 seconds,
wherein steps I-a1) and I-a2) are repeated in alternating turns for 10 to 25 times,
or
II-a) application of a noble metal compound, optionally in admixture with additives acting as promoters, and at the same time of a reducing agent to a support material, then drying at from 60 to 200° C. for 10 to 180 seconds,
wherein step II-a) is repeated for 10 to 25 times,
or
III-a2) application of the entire desired amount of a reducing agent to a support material, then drying at from 60 to 200° C. for 10 to 180 seconds, and
III-a3) application of the respective other compound,
b) optionally afterwards drying of the resulting product at from 100 to 350° C. for 2 to 180 minutes, and
c) subsequent calcination at from 350 to 550° C. for 15 minutes to 3 hours,
in an epoxidation or oxidative dehydrogenation.

2. The process according to claim 1 for oxidative dehydrogenation.

3. The process according to claim 1 for preparing olefinically unsaturated carbonyl compounds from olefinically unsaturated alcohols by oxidative dehydrogenation.

4. The process according claim 1 , wherein a noble metal compound selected from the group consisting of salts of Cu, Au, Ag, Pd, Pt, Rh, Ru, W, Os and mixtures thereof is used as noble metal compound.

5. The process according to claim 1 , wherein the reducing agent is selected from the group consisting of hydrazine, hydroxylamine, formaldehyde, ascorbic acid, urea, and mixtures thereof.

6. The process according to claim 1 , wherein the reducing agent is ascorbic acid, in the form of an aqueous solution.

7. The process according to claim 1 , wherein 3-methylbut-2-en-1-al and 3-methylbut-3-en-1-al are prepared from 3-methylbut-3-en-1-ol.

8. A process for producing a supported noble metal-comprising catalyst for epoxidation or oxidative dehydrogenation, comprising
I-a1) applying a noble metal compound, optionally in admixture with additives acting as promoters, to a support material, then drying at from 60 to 200° C. for 10 to 180 seconds,
and
I-a2) applying a reducing agent to a support material, then drying at from 60 to 200° C. for 10 to 180 seconds,
wherein steps I-a1) and I-a2) are repeated in alternating turns for 10 to 25 times,
or
II-a) applying a noble metal compound, optionally in admixture with additives acting as promoters, and at the same time of a reducing agent to a support material, then drying at from 60 to 200° C. for 10 to 180 seconds,
wherein step II-a) is repeated for 10 to 25 times,
or
III-a2) applying the entire desired amount of a reducing agent to a support material, then drying at from 60 to 200° C. for 10 to 180 seconds, and
III-a3) applying the respective other compound,
b) optionally afterwards drying the resulting product from 100 to 350° C. for 2 to 180 minutes, and
c) subsequently calcinining at from 350 to 550° C. for 15 minutes to 3 hours.

9. The process according to claim 8 , wherein a supported noble metal-comprising catalyst for the oxidative dehydrogenation of olefinically unsaturated alcohols is produced.

10. The process according to claim 8 , wherein a noble metal compound selected from the group consisting of salts of Cu, Au, Ag, Pd, Pt, Rh, Ru, W, Os and mixtures thereof is used as noble metal compound.

11. The process according to claim 8 , wherein a basic or acidic support material is used as support material.

12. The process according to claim 11 , wherein a support material selected from the group consisting of steatite, aluminium oxide, aluminosilicates and mixtures thereof is used as support material.

13. The process according to claim 8 , wherein the reducing agent is selected from the group consisting of hydrazine, hydroxylamine, formaldehyde, ascorbic acid, urea, and mixtures thereof.

14. A supported noble metal-comprising catalyst prepared by
I-a1) applying a noble metal compound, wherein the noble metal compound is selected from the group consisting of salts of Cu, Au, Ag, Pd, Pt, Rh, Ru, W, Os and mixtures thereof, optionally in admixture with additives acting as promoters, to a support material, then drying at from 60 to 200° C. for 10 to 180 seconds,
and
I-a2) applying a reducing agent, wherein the reducing agent is selected from the group consisting of hydrazine, hydroxylamine, formaldehyde, urea, ascorbic acid, and mixtures thereof, to a support material, then drying at from 60 to 200° C. for 10 to 180 seconds,
wherein steps I-a1) and I-a2) are repeated in alternating turns for 10 to 25 times,
or
II-a) applying a noble metal compound, wherein the noble metal compound is selected from the group consisting of salts of Cu, Au, Ag, Pd, Pt, Rh, Ru, W, Os and mixtures thereof, optionally in admixture with additives acting as promoters, and at the same time of a reducing agent, wherein the reducing agent is selected from the group consisting of hydrazine, hydroxylamine, formaldehyde, urea, ascorbic acid, and mixtures thereof, to a support material, then drying at from 60 to 200° C. for 10 to 180 seconds,
wherein step II-a) is repeated for 10 to 25 times,
or
III-a2) applying the entire desired amount of a reducing agent, wherein the reducing agent is selected from the group consisting of hydrazine, hydroxylamine, formaldehyde, urea, ascorbic acid, and mixtures thereof, to a support material, then drying at from 60 to 200° C. for 10 to 180 seconds, and
III-a3) applying the respective other compound,
b) optionally afterwards drying of the resulting product at from 100 to 350° C. for 2 to 180 minutes, and
c) subsequent calcination at from 350 to 550° C. for 15 minutes to 3 hours.

15. The catalyst according to claim 14 , wherein a support material selected from the group consisting of steatite, aluminium oxide, aluminosilicates and mixtures thereof is used as support material.

Assignees

• Basf Se

Inventors

• Huber Sabine
• Rosendahl Tobias
• Seeber Georg
• Baltes Christian

Classifications

• B01J23/30

  Tungsten · CPC title

• C07C45/29

  of hydroxy groups · CPC title

• B01J23/42

  Platinum · CPC title

• B01J23/02

  of the alkali- or alkaline earth metals or beryllium · CPC title

• B01J37/0219

  the coating containing organic compounds · CPC title