# US 10,865,461 B2 · Method for removing arsenic from materials containing same

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- Number: US 10,865,461 B2
- Document ID: US10865461B2
- Status: Granted
- Kind: B2
- Application number: 15/753,827
- Filed: 2015-09-02
- Published: 2018-08-30
- Granted: 2020-12-15
- Earliest claimed: 2015-09-02
- Assignees: Molibdenos Y Metales S.A.
- Applicants: Molibdenos y Metales S.A.
- Inventors: John Patrick Graell Moore; Manuel Enrique Guzman Manzo; Cristian Eduardo Pizarro Herrera; Christian Ignacio Soto Infante
- Web page: https://patentgrep.com/patent/US10865461B2

## CPC

- C22B 15/008: {with non-acid solutions containing salts of alkali or alkaline earth metals}
- C22B 3/12: in inorganic alkaline solutions
- C22B 30/04: Obtaining arsenic {(extraction of metal compounds by leaching in organic solutions C22B3/16; treatment or purification of solutions by adsorption on solids C22B3/24, by liquid-liquid extraction C22B3/26, by ion-exchange extraction C22B3/42)}
- Y02P 10/20: Recycling
- C22B: PRODUCTION AND REFINING OF METALS (electrolytic C25); PRETREATMENT OF RAW MATERIALS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Disclosed is a method for the removal of arsenic from materials containing a high arsenic content, or materials containing a high content of arsenic and selenium.

## Claims

### Claim 1

A process for the removal of arsenic from copper concentrates and/or copper cement with an arsenic content higher than 0.5% by dry weight or copper concentrates and/or copper cement with a high content of arsenic and selenium, comprising:
adding the copper concentrates and/or copper cement to a pressure reactor;
adding an alkaline leaching solution of a strong base selected from sodium hydroxide and potassium hydroxide dissolved in water to the pressure reactor;
adding an oxidizing gas to the pressure reactor;
mixing the above components in the pressure reactor to obtain a homogenous pulp and subjecting it to a pressure lixiviation that is selective for arsenic, wherein operation conditions of the pressure lixiviation are: temperature between 100° C. and 220° C., residence time of the pulp within the pressure reactor between 30 and 150 minutes, quantity of the leaching solution in the case of NaOH between 1.87 and 45.0 kg NaOH/kg As contained in the pulp, and oxidizing gas overpressure between 0 and 100 psig, wherein the dissolution of copper present in the copper concentrates and/or copper cement during said pressure lixiviation is less than 0.05% of the total copper, the dissolution of gold present in the copper concentrates and/or copper cement is less than 4% of the total gold and the dissolution of silver present in the copper concentrates and/or copper cement is less than 0.4% of the total silver;
subjecting the pulp obtained from the pressure lixiviation to a first solid-liquid separation step thereby separating a solid with low arsenic content and a liquor containing dissolved arsenic in its +5 oxidation state in the form of arsenate;
subjecting the liquor with dissolved arsenic to a precipitation of the arsenic with a precipitating agent that provides cations selected from Ce3+, Fe3+, Mg2+, or a combination of Fe3+ and Ca2+, said precipitating agent being selected from cerium chloride, ferric sulfate, magnesium sulfate, or ferric sulfate with addition of lime milk;
subjecting the product of the arsenic precipitation step to a second solid-liquid separation step, thereby obtaining a solid arsenic-containing product and an alkaline liquor free of arsenic.

### Claim 2 (depends on 1)

The process for the removal of arsenic according to claim 1, further comprising:
subjecting the alkaline liquor free of arsenic to a sodium sulfate (Na2SO4) crystallization step, thereby obtaining a pulp composed of Na2SO4 crystals and an alkaline liquor free of Na2SO4; and
subjecting the product of the Na2SO4 crystallization step to a third solid-liquid separation step, thereby obtaining a solid comprising Na2SO4 crystals and an alkaline liquor.

### Claim 3 (depends on 2)

The process for the removal of arsenic according to claim 2, wherein the alkaline liquor free of arsenic from the third solid-liquid separation step is partially or totally recirculated as part of the leaching solution of the pressure lixiviation, and the liquor that is not recirculated being subjected to a secondary arsenic elimination step of adsorption or ion exchange, or used as process water.

### Claim 4 (depends on 2)

The process for the removal of arsenic according to claim 2, wherein a fraction of the liquor with dissolved arsenic from the first solid-liquid separation step is recirculated to the pressure lixiviation while the other fraction is sent to the arsenic precipitation step, and the alkaline liquor free of arsenic from the third solid-liquid separation step is used as process water for recirculation.

### Claim 5 (depends on 1)

The process for the removal of arsenic according to claim 1, wherein a fraction of the alkaline liquor free of arsenic from the second solid-liquid separation step is recirculated to the pressure lixiviation while the other fraction is sent to an Na2SO4 crystallization step or sent to tailings.

### Claim 6 (depends on 2)

The process for the removal of arsenic according to claim 2, wherein the Na2SO4 crystallization step comprises a technique selected from the group consisting of continuous evaporation at constant volume, semi-continuous evaporation at constant volume, cooling, total evaporation of solvent, and evaporation in a solar pond.

### Claim 7 (depends on 1)

The process for the removal of arsenic according to claim 1, wherein the copper concentrates and/or copper cement to be treated also contains a high selenium content and the pressure lixiviation is selective for the dissolution of arsenic and selenium.

### Claim 8 (depends on 1)

The process for the removal of arsenic according to claim 1, wherein the oxidizing gas is selected from pure oxygen, enriched air, or air.

### Claim 9 (depends on 1)

The process for the removal of arsenic according to claim 1, wherein the pressure reactor is an autoclave, horizontal or vertical, with one or more stirrers, with one or more compartments separated by baffles, and with submerged or overhead injection of gas or both.

### Claim 10 (depends on 1)

The process for the removal of arsenic according to claim 1, wherein the mixing step is carried out by a repulping of the copper concentrates and/or copper cement with the alkaline leaching solution, and homogenizing the pulp to keep the percentage of solid within a range of 10-40% by weight.

### Claim 11 (depends on 1)

The process for the removal of arsenic according to claim 1, wherein when the oxidizing gas is air, the overpressure in the pressure reactor is 10-40 psig.

### Claim 12 (depends on 1)

The process for the removal of arsenic according to claim 1, wherein the pulp resulting from the pressure lixiviation has a pH of 10-14 and a redox potential greater than −0.5 V vs. SHE.

### Claim 13 (depends on 1)

The process for the removal of arsenic according to claim 1, wherein the solid-liquid separation steps are carried out by filtration, sedimentation, clarification, thickening, centrifugation, dewatering or decantation.

### Claim 14 (depends on 1)

The process for the removal of arsenic according to claim 1, wherein the solid with low arsenic content obtained from the first solid-liquid separation step is further subjected to a wash, where said wash liquor is sent to the arsenic precipitation step together with the mother liquor, and the washed solid is stored, or sent to a process of recovery of the remaining valuable components therein.

### Claim 15 (depends on 1)

The process for the removal of arsenic according to claim 1, wherein when the precipitating agent is CeCl3, the dose of the agent is 1.80-7.50 kg Ce3+/kg As and the precipitation is carried out at a pH of 6-12, and the pH is adjusted with H2SO4.

### Claim 16 (depends on 1)

The process for the removal of arsenic according to claim 1, wherein when the precipitating agent is Fe2(SO4)3, the dose of the agent is 0.70-8.0 kg Fe3+/kg As and the precipitation is carried out at a pH of 6-10, and the pH is adjusted with H2SO4.

### Claim 17 (depends on 16)

The process for the removal of arsenic according to claim 16, wherein the Fe2(SO4)3 is added directly, or is previously prepared from iron (II and III) oxide with H2SO4 or from ferrous sulfate (FeSO4) with H2O2, H2SO4 and hot water.

### Claim 18 (depends on 16)

The process for the removal of arsenic according to claim 16, wherein additionally lime milk is added to the Fe2(SO4)3 precipitating agent at a dose of 0.50-2.5 kg Ca2+/kg As.

### Claim 19 (depends on 1)

The process for the removal of arsenic according to claim 1, wherein when the precipitating agent is MgSO4, the dose of the agent is 0.45-1.50 kg Mg2+/kg As and the precipitation is carried out at a pH of 7-14, and the pH is adjusted with H2SO4.