Removal of arsenic from aqueous streams with cerium (IV) oxide compositions

• US 9,975,787 B2
• Filed: 03/09/2015
• Issued: 05/22/2018
• Est. Priority Date: 03/07/2014
• Status: Active Grant

• Current Assignee: Secure Natural Resources LLC (MP Materials Corp.)
• Original Assignee: Secure Natural Resources LLC (MP Materials Corp.)
• Inventors: Psaras, Dimitrios, Gao, Yuan, Haneline, Mason, Lupo, Joseph, Landi, Carol
• Primary Examiner(s): Gitomer, Ralph J
• Application Number:
  US14/642,446
• Publication Number:
  US 20150251927A1
• Time in Patent Office: 1,170 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 20/28016 Particle form
• CPC Class Codes: C02F 1/281 using inorganic sorbents
• CPC Class Codes: C02F 2101/103 Arsenic compounds
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]

Abstract

A cerium (IV) oxide composition having unexpectedly greater arsenic loading capacities than oxides of cerium (IV) of the prior art are disclosed. The arsenic loading capacities are greater at low level equilibrium levels of arsenic. The cerium (IV) oxide composition is more effective at removing arsenite and arsenate. Moreover, the cerium (IV) oxide composition has a greater capacity for the previously more difficult to remove arsenite.

Claims

1. A method for removing arsenic from an aqueous stream, comprising:

contacting a cerium (IV) oxide composition with an arsenic-containing aqueous stream, wherein the following are true;

(i) the cerium (IV) oxide composition has a zeta potential at about pH 7 of no more than about 16 mV and of more than about 1 mV;

(ii) the cerium (IV) oxide composition has a crystallite size of more than about 1 nm and less than about 19 nm;

(iii) the cerium (IV) oxide composition has an acidic site concentration of more than about 0.0001 acidic sites/kg and less than about 0.020 acidic sites/kg;

(iv) the cerium (IV) oxide composition has an isoelectric point of more than about pH 8.8; and

(v) the cerium (IV) oxide composition has an arsenic (III) removal capacity, at an initial concentration of arsenic (III) in the arsenic-containing aqueous stream of no more than about 440 ppb, of more than about 17.1 mg As(III)/g CeO₂,

wherein the contacting of the cerium (IV) oxide composition with the arsenic-containing aqueous stream removes some of the arsenic from the arsenic-containing aqueous stream.

2. The method of claim 1, wherein the arsenic comprises one or both of arsenite and arsenate.

3. The method of claim 2, wherein the cerium (IV) oxide composition has a loading capacity for arsenite of from 2.1 to about 6.0 mg/g for an equilibrium arsenite concentration of from about 0.5 to about 5 ppb and wherein the cerium (IV) oxide composition has a loading capacity for arsenate of from 0.1 to about 0.2 mg/g for an equilibrium arsenate concentration of from about 0.5 to about 2.5 ppb.

4. The method of claim 1, wherein one or more of the following is true:

(v) the cerium (IV) oxide composition has a zeta potential at about pH 7 of more than about 7.5 mV and no more than about 12.5 mV;

(vi) the cerium (IV) oxide composition has a particle size D₁₀ of more than about 0.5 μ

m and no more than about 4 μ

m;

(vii) the cerium (IV) oxide composition has a particle size D₅₀ of more than about 2 μ

m and no more than about 20 μ

m; and

(viii) the cerium (IV) oxide composition has a particle size D₉₀ of more than about 12 μ

m and no more than about 50 μ

m.

5. The method of claim 1, wherein the cerium (IV) oxide composition comprises rare earth oxides other than Ce (IV)O₂ and wherein the rare earth oxides other than Ce (IV)O₂ comprise no more than about 40 wt % of the cerium (IV) oxide composition.

6. The method of claim 1, wherein the cerium (IV) oxide lacks any added non-rare earth materials comprising one or more silicon, titanium and zirconium.

7. The method of claim 1, wherein the cerium (IV) oxide composition has a loading capacity for arsenite of from 2.1 to about 6.0 mg/g for an equilibrium arsenite concentration of from about 0.5 to about 5 ppb.

8. The method of claim 1, wherein the cerium (IV) oxide composition has a loading capacity for arsenate of from 0.1 to about 0.2 mg/g for an equilibrium arsenate concentration of from about 0.5 to about 2.5 ppb.

9. A method for removing arsenic from an aqueous stream, comprising:

contacting a cerium (IV) oxide composition with an arsenic-containing aqueous stream, wherein the following conditions are true;

(i) the cerium (IV) oxide composition has a zeta potential at about pH 7 of no more than about 16 mV and of more than about 1 mV;

(ii) the cerium (IV) oxide composition has an acidic site concentration of more than about 0.0001 acidic sites/kg and less than about 0.020 acidic sites/kg;

(iii) the cerium (IV) oxide composition has an isoelectric point of more than about pH 8.8;

(iv) the cerium (IV) oxide composition has at least one of;

(a) a particle size D₁₀ of more than about 0.5 μ

m and no more than about 4 μ

m;

(b) a particle size D₅₀ of more than about 2 μ

m and no more than about 20 μ

m; and

(c) a particle size D₉₀ of more than about 12 μ

m and no more than about 50 μ

m; and

(v) the cerium (IV) oxide composition has an arsenic (III) removal capacity, at an initial concentration of arsenic (III) in the arsenic-containing aqueous stream of no more than about 440 ppb, of more than about 17.1 mg As(III)/g CeO₂,

wherein the contacting of the cerium (IV) oxide composition with the arsenic-containing aqueous stream removes some of the arsenic from the arsenic-containing aqueous stream.