Method for the purification of metal-containing aqueous media and method of preparing an adsorbent

• US 5,635,073 A
• Filed: 04/12/1995
• Issued: 06/03/1997
• Est. Priority Date: 09/18/1992
• Status: Expired due to Term

• Current Assignee: Kruger AS (Veolia Environnement SA)
• Original Assignee: Kruger AS (Veolia Environnement SA)
• Inventors: Aktor, Henrik, Christensen, Terkel C.
• Primary Examiner(s): McCarthy, Neil
• Application Number:
  US08/403,713
• Time in Patent Office: 783 Days
• Field of Search: 210/721, 210/722, 210/714, 210/713, 210/712, 210/912, 210/913, 210/720
• US Class Current: 210/714
• CPC Class Codes: B01D 2215/021 Physically moving or fluidising the adsorbent beads or particles or slurry, excluding the movement of the entire columns
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: C02F 1/281 using inorganic sorbents
• CPC Class Codes: C02F 1/72 by oxidation C02F1/4672 takes precedence
• CPC Class Codes: C02F 1/722 Oxidation by peroxides
• CPC Class Codes: C02F 1/76 with halogens or compounds of halogens C02F1/4674 takes precedence
• CPC Class Codes: C02F 1/78 with ozone C02F1/4672 takes precedence
• CPC Class Codes: C02F 2101/20 Heavy metals or heavy metal compounds
• CPC Class Codes: Y10S 210/912 Heavy metal
• CPC Class Codes: Y10S 210/913 Chromium

Abstract

A method for the removal of metal from a metal-containing aqueous medium wherein the aqueous medium is passed through a particulate carrier material in the presence or ferrous iron and an oxidant and at such velocity and in such direction that the carrier material particles are fluidised in the aqueous medium and wherein metal-containing coatings are formed on the surfaces of the carrier material particles and wherein the particles thus coated are separated from the aqueous medium. A method for the production of iron oxyhydroxide-containing adsorbent wherein the carrier material particles are fluidised in an aqueous medium in the presence ferrous iron and an oxidant so as to form iron oxyhydroxide coatings on the particles and wherein the particles thus formed are separated from the aqueous medium.

Claims

1. A method for the removal of dissolved heavy metal ions from a metal-containing aqueous medium wherein the aqueous medium is contacted with a particulate carrier material so as to form a metal-containing iron hydroxide coating on the carrier material particles and wherein the coated carrier material particles are separated from the aqueous medium, the method comprising the steps of:

(a) introducing a volume of carrier material particles into a reactor;

(b) directing the metal-containing aqueous medium into the reactor in the presence of dissolved ferrous ions;

(c) introducing an oxidant into the aqueous medium;

(d) fluidising the carrier material particles in the reactor by passing the aqueous medium through the reactor at such a velocity and in such a direction as to fluidise the carrier material particles;

(e) forming an iron oxyhydroxide coating on the carrier material particles by oxidizing the ferrous ions and hydrolyzing the resulting ferric ions;

(f) adsorbing heavy metal ions onto outer surfaces of the carrier material particles; and

(g) separating and removing the carrier material particles having the heavy metal ions adsorbed thereon from the aqueous medium.

2. The method according to claim 1, wherein a particulate inert material is used as the carrier material.

3. The method according to claim 2, wherein sand grains are used as the carrier material.

5. The method according to claim 1, wherein the carrier material particles have a mean diameter of from 0.1 to 2.5 mm.

6. The method according to claim 1, further comprising the step of maintaining a pH-value of from 2.5 to 8.5 in the aqueous medium.

7. The method according to claim 1, wherein the aqueous medium comprises one of the following group:

process waste water, drinking water, and ground water.

8. The method according to claim 1, wherein the oxidant comprises one of the following group:

oxygen, ozone, chlorine, chloroxide, hydrogen peroxide, sodium permanganate, chromates, and dichromates.

9. The method according to claim 1, wherein the dissolved metal ions are ferrous iron in the form of a ferrous salt selected from the group consisting of ferrous sulfate and ferrous chloride.

10. The method according to claim 1, wherein the dissolved metal ions comprise ferrous iron and chromium(VI), and further comprising the steps of:

adsorbing the ferrous iron and the chromium(VI) on the carrier material particles;

oxidizing the ferrous iron to ferric iron while simultaneously reducing the chromium(VI) to chromium(III);

hydrolyzing the ferric iron and chromium(III); and

forming a Fe(III)- and Cr(III)-oxyhydroxide coating on the carrier material particles.

11. The method according to claim 1, including the step of continuously removing from the reactor the carrier material particles having heavy metal ions adsorbed thereon.

12. The method according to claim 1, including the steps of oxidizing the metal ions adsorbed on the carrier material particles and hydrolyzing the oxidized metal ions to form a metal-containing hydroxide coating on the carrier material particles.

4. A method for the production of an iron oxyhydroxide-containing adsorbent wherein iron oxyhydroxide is bonded to the surface of carrier material particles, comprising the steps of:

passing an aqueous medium containing dissolved ferrous iron and an oxidant through the carrier material particles at such velocity and in such direction that the carrier material particles are fluidised in the aqueous medium, forming dense coatings of iron oxyhydroxide in-situ on the carrier material particles, and separating the particles thus coated from the aqueous medium.

13. A method for the continuous removal of dissolved heavy metal ions from wastewater, comprising the steps of:

(A) introducing a volume of carrier material particles into a reactor vessel;

(b) introducing wastewater containing dissolved heavy metal ions into the reactor vessel in the presence of dissolved ferrous ions;

(c) passing the wastewater through the reactor vessel at such a velocity and in such a direction as to fluidize the carrier material particles;

(d) introducing an oxidant into the wastewater, said oxidant oxidizing the ferrous ions to ferric ion, hydrolyzing the ferric ion into iron oxyhydroxide thereby forming in-situ an iron oxyhydroxide coating on the outer surfaces of the carrier material particles;

(e) adsorbing metal ions onto outer surfaces of the carrier material particles coated with said iron oxyhydroxide coating;

(f) oxidizing the metal ions adsorbed on the carrier material particles;

(g) hydrolyzing the oxidized metal ions to form a metal-containing hydroxide coating on the carrier material particles;

(h) adsorbing additional metal ions on the metal-containing hydroxide coating, thereby increasing the thickness of the metal-containing hydroxide coating; and

(i) continuously separating the coated carrier material particles from the wastewater, thereby removing the metal ions from the wastewater.

14. The method according to claim 13, wherein the dissolved metal ions comprise ferrous iron and chromium(VI), and further comprising the steps of:

adsorbing the ferrous iron and the chromium(VI) on the carrier material particles;

oxidizing the ferrous iron to ferric iron while simultaneously reducing the chromium(VI) to chromium(III);

hydrolyzing the ferric iron and chromium(III); and

forming a Fe(III)- and Cr(III)-oxyhydroxide coating on the carrier material particles.

15. The method according to claim 13, wherein a single reactor vessel is used for all steps of separating dissolved heavy metal ions from the wastewater.

16. The method according to claim 15, wherein the step of separating the coated carrier material particles from the wastewater includes continuously removing the particles through an outlet in the reactor vessel as the particles achieve metal-containing hydroxide coatings of a suitable thickness.