Method for producing finely divided haematite and for producing iron oxide red pigments

Patent metadata

Field	Value
Publication number	US-9428402-B2
Application number	US-201214342860-A
Country	US
Kind code	B2
Filing date	Sep 28, 2012
Priority date	Sep 30, 2011
Publication date	Aug 30, 2016
Grant date	Aug 30, 2016

Abstract

The present invention relates to an improved process for the production of finely divided haematite and of iron oxide red pigments made up of the finely divided haematite and the use of the finely divided haematites and iron oxide red pigments produced by this process.

First claim

What is claimed is:

1. A process for the production of finely divided haematit having a particle size of less than or equal to 100 nm and a specific BET surface area of 40 m 2 /g to 150 m 2 /g, measured in accordance with DIN 66131, the process comprising:
a) adding dilute nitric acid to a mixture of metallic iron and water at a temperature of 60 to 120° C. to produce a reaction mixture, wherein the dilute nitric acid is added at a rate sufficient to raise the temperature of the reaction mixture to a temperature of 105 to 160° C., producing an aqueous suspension of finely divided haematite, and
b) separating the aqueous suspension of finely divided haematite from any unreacted, metallic iron.

2. The process according to claim 1 , wherein the dilute nitric acid is added at a rate of addition sufficient to raise the temperature of the reaction mixture by at least 15° C. within less than 120 minutes after the addition of nitric acid is complete.

3. The process according to claim 1 , further comprising isolating the finely divided haematite from the aqueous suspension.

4. A process for the production of finely divided haematite having a particle size of less than or equal to 100 nm and a specific BET surface area of 40 m 2 /g to 150 m 2 /g, measured in accordance with DIN 66131, the process comprising:
a) heating a mixture of metallic iron and water to a temperature of 60 to 120° C. in a closed, pressure-tight vessel to produce a heated mixture,
b) adding dilute nitric acid to the heated mixture of step a) to produce a reaction mixture, wherein the dilute nitric acid is added at a rate of addition sufficient to raise the temperature of the reaction mixture by at least 15° C. within less than 120 minutes after the addition of nitric acid is complete, and reacting the nitric acid and metallic iron with a corresponding pressure increase in the vessel to a pressure greater than atmospheric pressure, wherein the reaction mixture reaches a temperature of 105 to 160° C. without supply of external heat, and whereby an aqueous suspension of finely divided haematite is produced, and
c) separating the aqueous suspension of finely divided haematite from the metallic iron.

5. The process according to claim 1 , wherein the finely divided haematite has a particle size of 20 to 100 nm.

6. The process according to claim 4 , wherein the heating of a mixture of metallic iron and water in step a) comprises heating to 75 to 120° C.

7. The process according to claim 4 , wherein the pressure in the closed vessel rises to 0.2 to 1 MPa in step b).

8. The process according to claim 1 , wherein a mol ratio of Fe to HNO 3 is from 1.33:1 to 16:1.

9. The process according to claim 1 , wherein a mol ratio of Fe to HNO 3 is from 1.5 to 4.

10. The process according to claim 1 , wherein a mol ratio of Fe to HNO 3 is from 1.33 to 1.8.

11. The process according to claim 1 , wherein the dilute nitric acid has a concentration of 10 to 67% by weight of HNO.

12. The process according to claim 1 , wherein:
the finely divided haematite has a particle size of 30 to 90 nm and a BET surface area of 60 m 2 to 120 m 2 /g;
the metallic iron and water in step a) is heated to 75 to 95° C.;
adding the dilute nitric acid comprises adding 2 to 15 wt % of HNO 3 based on the weight of the reaction mixture wherein the dilute nitric acid has a concentration of 20 to 67% by weight of HNO 3 ;
the reaction mixture is contained in a closed pressure vessel and reaches a temperature of 120 to 160° C., and a pressure of 0.2 to 1 MPa;
the dilute nitric acid is added a rate of addition sufficient to raise the temperature of the reaction mixture by at least 30° C. within less than 90 minutes after the addition of nitric acid is complete; and
the process further comprises, prior to separating the a aqueous suspension, cooling the reaction mixture to a temperature less than 100° C.

13. A process for production of iron oxide red pigments, the process comprising:
i. production of an aqueous suspension of finely divided haematite according to the process of claim 1 , and
ii. reacting the aqueous suspension of finely divided haematite as nucleus with:
an iron salt and an alkaline precipitate in the presence of oxygen-containing gases or
an elemental iron, an iron salt and oxygen-containing gases to give haematite pigment suspension.

14. The process for the production of iron oxide red pigments according to claim 13 , wherein, when the reaction of the aqueous suspension of finely divided haematite as nucleus with an iron salt in step ii) is carried out in the presence of metallic iron, metallic iron is used in step ii) in a concentration of 20 to 100 g/l based on the volume of the reaction mixture at the beginning of the reaction.

15. The process for the production of iron oxide red pigments according to claim 13 , wherein:
the aqueous suspension of finely divided haematite as nucleus is reacted with an iron salt and an alkaline precipitant in the presence of oxygen-containing gases, and
the oxygen-containing gases are introduced into the reaction mixture in an amount of 1 to 30 liters per hour per liters of reaction volume (liters/hour/liters) for a time of 2 to 150 hours during heating up to the reaction temperature and/or during the reaction.

16. Finely divided haematite obtained by the process according to claim 1 .

17. Iron oxide red pigment obtained according to the process of claim 13 .

18. A process for the colouring of products of the paint, varnish, coatings, building material, plastics or paper industry, of foodstuffs, baking enamels or coil coating compositions, granulated sands, sand-lime bricks, enamels, ceramic glazes, asphalt or bark mulch or of products of the pharmaceutical industry, which process comprises:
x. production of the finely divided haematite according to claim 1 , and
y. colouring products of the paint, varnish, coatings, building material, plastics or paper industry, of foodstuffs, baking enamels or coil coating compositions, granulated sands, sand-lime bricks, enamels, ceramic glazes, asphalt or bark mulch or of products of the pharmaceutical industry, by means of the finely divided haematite of step x).

19. The process according to claim 4 , further comprising isolating the finely divided haematite from the aqueous suspension.

20. The process for the production of iron oxide red pigments according to claim 15 , wherein the oxygen-containing gas is air.

Assignees

• Lanxess Deutschland Gmbh

Inventors

• Ketteler Guido
• Holtmann Udo
• Kischkewitz Juergen

Classifications

• C01P2006/12

  Surface area · CPC title

• B82Y30/00

  Nanotechnology for materials or surface science, e.g. nanocomposites · CPC title

• Y10T428/2982

  Particulate matter [e.g., sphere, flake, etc.] · CPC title

• C01G49/06 Primary

  Ferric oxide [Fe2O3] · CPC title

• C09C1/24

  Oxides of iron · CPC title