Method for preparing a catalyst

Patent metadata

Field	Value
Publication number	US-10569258-B2
Application number	US-201515536231-A
Country	US
Kind code	B2
Filing date	Dec 21, 2015
Priority date	Dec 19, 2014
Publication date	Feb 25, 2020
Grant date	Feb 25, 2020

Abstract

The invention relates to a method for preparing a catalyst or catalyst precursor comprising a catalytically active material and a carrier material. The invention relates to a catalyst particle and catalyst precursor thereof obtainable by said method. The catalyst may be used in a process for synthesising hydrocarbons.

First claim

That which is claimed is:

1. A method for preparing a hydrogenation catalyst comprising a catalytically active material and a carrier material, the method comprising,
a. providing an acidic solution comprising cobalt ions;
b. providing a suspension comprising the carrier material; and
c. providing an alkaline solution; and
d. mixing the acidic solution, the suspension and the alkaline solution causing the cobalt to precipitate in the presence of the carrier material, obtaining a mixture comprising a precipitate;

wherein the acidic solution comprises a carboxylic acid or a conjugated base thereof having a pKa value in the range of 3.0-6.5.

2. The method according to claim 1 , wherein the carboxylic acid or a conjugated base thereof comprises at least one carboxylic acid group and the carboxylic acid has a hydroxyl group on the alpha carbon position.

3. The method according to claim 1 , wherein the carboxylic acid or a conjugated base thereof has 2 or more carboxylic groups and at least 2 of the carboxylic acid groups have a pKa values in the range of 4.0-6.5.

4. The method according to claim 1 , wherein the carboxylic acid or a conjugated base thereof is selected from the group consisting of citric acid, malic acid, tartaric acid, gluconic acid and combinations thereof.

5. The method according to claim 1 wherein, the molar ratio of the carboxylic acid or a conjugated base thereof, to the cobalt is maximally 1:5 during mixing.

6. The method according to claim 1 , wherein during step d. the pH of the mixture is raised to a pH of at least 5.5.

7. The method according to claim 1 , wherein the temperature of the mixture is maintained at a temperature of maximally 100° C.

8. The method according to claim 1 , further comprising a step e. wherein:
e. the precipitate obtained in step d. is separated from the mixture, by means of filtration over a filter press, to obtain a catalyst precursor as a retentate; and drying the retentate; and comprising a step of:
f. washing the retentate at least once with a washing medium, preferably water.

9. The method according to claim 1 , wherein the alkaline solution is added after the start of mixing of the acidic solution and the suspension, the alkaline solution is added after completion of the mixing of the acidic solution and the suspension.

10. The method according to claim 1 , wherein the method is conducted batch wise such that first the alkaline solution is added to the suspension until the mixture reaches a pH of 5.5 or higher, continuing the addition of the alkaline solution to the suspension while simultaneously adding the acidic solution and mixing.

11. The method according to claim 1 , wherein the alkaline solution comprises a carbonate containing salt, or a combination of said carbonate salt with another base; wherein the alkaline solution is added in step d. such that molar ratio of CO3: cobalt is at least 0.5.

12. A precursor of a hydrogenation catalyst comprising a metal salt of cobalt, on a carrier material, wherein the precursor after calcination comprises crystallites of cobalt oxides having a crystallite size of maximally 8 nm as measured with XRD, wherein the precursor is prepared according to the method of claim 1 .

13. The precursor according to claim 12 , wherein the cobalt is present as cobalt hydroxyl carbonate, cobalt hydroxide and/or cobalt hydroxycarbonate.

14. The precursor according to claim 13 , wherein maximally 6% of the cobalt is present in clusters having an equivalent diameter of 100 nm or larger and in which a cluster is defined as a region in which the cobalt content is at least 125% of the average metal content of the sample.

15. The precursor according to claim 14 , wherein the precursor has a BET value and the metal in its oxidic state contributes to the total BET value of the precursor upon oxidation of maximum 350° C. in an amount of at least 120 m 2 /gram metal, and/or said precursor has a metal surface area after reduction which is at least 35 m 2 /gram material.

Assignees

• Shell Oil Co

Inventors

• Klemt Andreas
• Domokos László
• FRIEDEL Frank Peter
• Boettcher Stefan
• Stobbe Erwin Roderick

Classifications

• B01J23/75 Primary

  Cobalt · CPC title

• B01J37/16

  Reducing · CPC title

• B01J23/745

  Iron · CPC title

• C10G2/332

  of the iron-group · CPC title

• B01J23/74

  Iron group metals · CPC title