Agent for adsorption of ruthenium from aqueous solution and method for adsorption of ruthenium from aqueous solution

• US 10,449,510 B2
• Filed: 03/22/2016
• Issued: 10/22/2019
• Est. Priority Date: 03/24/2015
• Status: Active Grant

• Current Assignee: Clariant Catalysts (Japan) K.K. (Nissan Chemical Corporation)
• Original Assignee: Clariant Catalysts (Japan) K.K. (Nissan Chemical Corporation)
• Inventors: Nakashima, Tadahito, Kim, Hyun-Joong, Sakuma, Takashi, Komatsu, Makoto, Izumi, Takeshi
• Primary Examiner(s): Barry, Chester T
• Application Number:
  US15/560,348
• Publication Number:
  US 20180071712A1
• Time in Patent Office: 1,309 Days
• Field of Search: None
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/28011 Other properties, e.g. density, crush strength
• CPC Class Codes: B01J 20/2803 Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
• CPC Class Codes: B01J 20/28057 Surface area, e.g. B.E.T specific surface area
• CPC Class Codes: C01B 33/113 Silicon oxides; Hydrates thereof preparing monoxide by reduction of siliceous material C01B33/182
• CPC Class Codes: C01F 7/02 Aluminium oxide; Aluminium hydroxide; Aluminates
• CPC Class Codes: C01G 45/02 Oxides; Hydroxides
• CPC Class Codes: C01G 55/00 Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
• CPC Class Codes: C02F 1/28 by sorption using ion-exchange C02F1/42; sorbent compositions B01J
• CPC Class Codes: C02F 1/281 using inorganic sorbents
• CPC Class Codes: C02F 2101/006 Radioactive compounds
• CPC Class Codes: C02F 2101/20 Heavy metals or heavy metal compounds
• CPC Class Codes: C22B 11/00 Obtaining noble metals
• CPC Class Codes: G01N 23/20075 by measuring interferences of X-rays, e.g. Borrmann effect

Abstract

An adsorbent is provided to adsorb ruthenium from aqueous solution for recovery and/or reuse or removal of said ruthenium, and a method for purifying, for example, sea water and/or water containing sodium ions, magnesium ions, calcium ions, chlorine ions or other ions, polluted with a radioactive element, using said adsorbent.

The ruthenium adsorbent includes manganese in the form of oxides thereof. The adsorbent can further include at least one additional transition metal element other than manganese, such as copper. The adsorbent soaked in water removes radioactive ruthenium or the like through adsorption, and thereby can purify, for example, sea water and/or water containing sodium ions, magnesium ions, calcium ions, chlorine ions or other ions.

Claims

1. A ruthenium adsorbent comprising manganese oxides as the primary component of the adsorbent, provided that manganese oxides consisting of ε

-MnO₂ and/or γ

-MnO₂ are excluded from the manganese oxides,

wherein the manganese oxides have an amorphous structure or a layered structure or a tunnel structure, and

wherein, in the case that the manganese oxides have a tunnel structure, the adsorbent comprises an oxide of manganese having at least two linked MnO₆ octahedrons forming each horizontal and vertical side of the tunnel structure.

2. The ruthenium adsorbent according to claim 1, wherein the manganese oxides have an amorphous structure and/or α

-MnO₂ and/or δ

-MnO₂.

3. The ruthenium adsorbent according to claim 1, wherein the manganese oxides have an amorphous structure and/or α

-MnO₂.

4. The ruthenium adsorbent according to claim 1, wherein a content of manganese calculated as manganese dioxide is 50 parts by weight or more, based on 100 parts by weight of the adsorbent.

5. The ruthenium adsorbent according to claim 1, further comprising at least one additional transition metal element other than manganese.

6. The ruthenium adsorbent according to claim 5, wherein the at least one additional transition metal element is in the form of oxides thereof.

7. The ruthenium adsorbent according to claim 6, wherein manganese and the at least one additional transition metal element are present in the form of a physical mixture of manganese oxides and oxides of the at least one additional transition metal element.

8. The ruthenium adsorbent according to claim 6, wherein manganese and the at least one additional transition metal element are present in the form of composite oxides thereof.

9. The ruthenium adsorbent according to claim 7, wherein a weight ratio of manganese oxides to oxides of the at least one additional transition metal is 1:

0.001 to 1;

1, when the weight of the manganese oxides is calculated as the weight of manganese dioxide.

10. The ruthenium adsorbent according to claim 8, wherein the molar ratio of manganese to the at least one additional transition metal element is 1:

0.001 to 1;

1.

11. The ruthenium adsorbent according to claim 5, wherein the at least one additional transition metal element is selected from the group consisting of iron, cobalt, copper and zinc.

12. The ruthenium adsorbent according to claim 1, having a specific surface area of 70 to 700 m²/g.

13. The ruthenium adsorbent according to claim 1, in the form of a powder.

14. The ruthenium adsorbent according to claim 1, in the form of a shaped article.

15. The ruthenium adsorbent according to claim 1, further comprising an inorganic binder which comprises a metal element other than transition metals and/or a metalloid element.

16. The ruthenium adsorbent according to claim 15, wherein the inorganic binder comprises aluminum oxides or silicon oxides.

17. A method for recovering ruthenium from waste fluid discharged from a production line for industrial products and/or a recycling process for industrial products, comprising contacting the waste fluid with the ruthenium adsorbent according to claim 1, wherein the waste fluid contains ruthenium.

18. A method of removing ruthenium from a ruthenium-containing aqueous solution, comprising the steps of contacting the ruthenium-containing water with the ruthenium adsorbent according to claim 1.

19. The method according to claim 18, wherein the aqueous solution comprises ruthenium in the form of a ruthenium cation, and/or a ruthenium complex ion and/or a ruthenate ion.

20. The method according to claim 18, wherein the ruthenium-containing aqueous solution comprises radioactive ruthenium.

21. The method according to claim 18, wherein the ruthenium-containing aqueous solution comprises sea water and/or water containing an ion selected from the group consisting of a sodium ion, a magnesium ion, a calcium ion, a chlorine ion and other ions, and wherein the aqueous solution further comprises a radioactive element including radioactive ruthenium.