Method for preparing solids from a mixture of at least one malachite powder and an oxide powder and the use of said solids

Patent metadata

Field	Value
Publication number	US-11241667-B2
Application number	US-201816005907-A
Country	US
Kind code	B2
Filing date	Jun 12, 2018
Priority date	Jun 13, 2017
Publication date	Feb 8, 2022
Grant date	Feb 8, 2022

Abstract

The invention relates to a method for preparing a solid comprising the mixture of a set of compounds comprising at least one Cu2(OH)2CO3 powder, one metal oxide powder selected from the group of metals consisting of copper, zinc, iron, manganese and mixtures thereof, and at least one binder as well as the use of the solid prepared by means of this method.

First claim

The invention claimed is:

1. A method for preparing a solid, comprising the steps of:
a) mixing of a set of compounds comprising at least one malachite Cu 2 (OH) 2 CO 3 powder, at least one metal oxide powder selected from the group consisting of copper, zinc, iron, manganese and mixtures thereof, and at least one binder, thereby forming a mixture;
b) contacting the mixture of step a) with an aqueous solution to obtain a paste and kneading the paste;
c) extruding the paste kneaded in step b) at a pressure of between 3 and 25 MPa thereby obtaining extrudates; and
d) calcinating the extrudates at a temperature between 140° C. and 500° C. and for a duration between 10 minutes and 6 hours under a gaseous flow comprising oxygen;
wherein when the at least one metal oxide powder included in said set of compounds of said step a) is copper oxide, said set of compounds is free from zinc oxide,
wherein the solid exhibits an EGG (grain by grain crushing test) value greater than 0.7 daN·mm −1 and a sulfur capture capacity greater than 0.16 grams of sulfur/gram of solid, wherein the EGG value described by American Society for Testing and Materials (ASTM) D 6175-3 method, and
wherein the sulfur capture capacity is determined by a test carried out at a temperature of 50° C., at a pressure of 0.3 MPa, and with an hourly volume velocity of 1530 h −1 , a gas used for the test contains 0.9 vol % H 2 S in nitrogen, and a content of H 2 S present in an outlet gas from a reactor by gas chromatography.

2. The method for preparing a solid according to claim 1 , wherein the extrudates obtained from step c) are dried at a temperature between 70 and 160° C. for a duration between 1 and 24 hours before being calcinated in step d).

3. The method for preparing a solid according to claim 1 , wherein a content of said at least one metal oxide powder expressed as a ratio of a mass of said at least one metal oxide powder introduced into the set of compounds mixed in step a) to a total mass of the at least one malachite Cu 2 (OH) 2 CO 3 powder and said at least one metal oxide powder introduced into the set of compounds mixed in step a) is between 0.01 and 1.

4. The method for preparing a solid according to claim 1 , wherein said at least one malachite Cu 2 (OH) 2 CO 3 powder has a bimodal distribution.

5. The method for preparing a solid according to claim 4 , wherein said at least one malachite Cu 2 (OH) 2 CO 3 powder comprises 0.1 to 99.9 wt % of malachite particles with a D 50 between 1 and 15 μm, and 99.9 to 0.1 wt % of malachite particles with a D 50 between 25 and 100 μm, the weight percentage being expressed relative to a total weight of said at least one malachite Cu 2 (OH) 2 CO 3 powder.

6. The method for preparing a solid according to claim 1 , wherein the solid exhibits the EGG value between 0.9 and 1.8 daN·mm −1 and the sulfur capture capacity between 0.19 and 0.27 grams of sulfur/gram of solid.

7. The method for preparing a solid according to claim 1 , wherein said aqueous solution of step b) contains an acid or base peptizing agent.

8. The method for preparing a solid according to claim 7 , wherein said aqueous solution contains nitric acid, with a ratio of mass of HNO 3 mass to mass of said at least one metallic oxide powder is between 0.5 and 10.

9. The method for preparing a solid according to claim 7 , wherein said basic peptizing agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, aqueous ammonia, tetraethylammonium hydroxide, ammonium carbonate and mixtures thereof, and a ratio of the basic peptizing agent to mass of said at least one metal oxide powder is between 1 and 10.

10. The method for preparing a solid according to claim 1 , wherein the aqueous solution of step b) is deionized water.

11. The method for preparing a solid according to claim 1 , wherein step d) of calcination is carried out at a temperature between 200° C. and 500° C.

12. The method for preparing a solid according to claim 1 , wherein the at least one binder is a bentonite clay.

13. The method for preparing a solid according to claim 1 , wherein the prepared solid has a content of the at least one binder between 15 wt % and 25 wt % of the solid.

14. The method for preparing a solid according to claim 1 , wherein the at least one binder is a kaolinite mineral, a palygorskite mineral, a smectite clay mineral, alumina, a precursor of alumina, silica or a mixture thereof.

15. The method for preparing a solid according to claim 1 , wherein said at least one metal oxide powder included in the set of compounds of the said step a) is zinc oxide, and said set of compounds being free of copper oxide.

Assignees

• Axens
• Ifp Energies Now

Inventors

• Bazer-Bachi Delphine
• Chiche David
• Lopez Joseph
• Serres Thomas
• Frising Tom
• Ducreux Olivier
• Euzen Patrick

Classifications

• B01D53/48

  Sulfur compounds · CPC title

• B01D2257/553

  Compounds comprising hydrogen, e.g. silanes · CPC title

• B01J20/3042

  Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent · CPC title

• B01D2257/30

  Sulfur compounds · CPC title

• B01D2257/502

  Carbon monoxide · CPC title