CN108570684B - Electrochemical treatment method of arsenic-containing soot - Google Patents

Electrochemical treatment method of arsenic-containing soot Download PDF

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CN108570684B
CN108570684B CN201710145148.8A CN201710145148A CN108570684B CN 108570684 B CN108570684 B CN 108570684B CN 201710145148 A CN201710145148 A CN 201710145148A CN 108570684 B CN108570684 B CN 108570684B
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CN108570684A (en
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金伟
薛玉冬
郑诗礼
张懿
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Institute of Process Engineering of CAS
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Abstract

The invention provides an electrochemical treatment method of arsenic-containing soot, which comprises the following steps: (1) mixing an alkali and a solvent or an alkali solution with the arsenic-containing soot to obtain a mixture; (2) placing the mixture as an electrolyte in an electrochemical reaction device for electrochemical reaction, wherein oxidizing gas is introduced into the electrolyte in the electrochemical reaction process; (3) and (3) carrying out solid-liquid separation on the reaction product obtained in the step (2) to obtain an arsenic-containing solution. The method has the advantages of high arsenic extraction rate, cleanness, no pollution, mild process conditions, low cost and low requirement on equipment; no impurity is introduced, so that the subsequent separation is facilitated; the concentration of the used alkali is lower, so that the alkali consumption is reduced; the automation degree is high, the manpower input can be reduced, good economic benefits and social benefits can be brought, and the application prospect is good.

Description

Electrochemical treatment method of arsenic-containing soot
Technical Field
The invention belongs to the technical field of pollutant treatment, and relates to an electrochemical treatment method of arsenic-containing soot.
Background
Arsenic compounds are chemical substances with high toxicity to organisms, are internationally recognized carcinogenic factors, are countries with serious arsenic damage in China, and cause severe social influence. Arsenic belongs to a sulfur-philic metalloid or semimetal element, mainly exists in the form of sulfide, sulfur arsenide, arsenate and the like in natural minerals, is mainly produced in non-ferrous metal deposits as associated ores of other metals, is enriched in a smelting or production manufacturing process, and gradually forms high-toxicity arsenic-containing solid waste.
Arsenic also has special application in the fields of agriculture, electronics, medicine, metallurgy, chemical industry and the like, and can be used for preparing pesticides, wood preservatives, glass clarifying decolorants and the like. During the smelting of arsenic and the production and use of compounds thereof, a large amount of arsenide is introduced into the environment, so that the water source is polluted and the human health is harmed. China 'industrial enterprise sanitary Standard' stipulates: the maximum allowable mass concentration of arsenic in ground water is 0.04mg/L, and the daily average maximum allowable mass concentration of arsenide in atmosphere of residential area is 0.003mg/m3. The emission of industrial three wastes is regulated by a trial standard: the maximum allowable mass concentration of arsenic and inorganic compounds thereof is 0.5 mg/L. By adopting the modern wastewater treatment technology, the arsenic-containing wastewater can be discharged up to the standard easily, however, the pollution and harm of solid arsenic-containing waste generated in the smelting process, arsenic-containing sediments generated in the treatment of wastewater and waste acid to the environment are not thoroughly cured, a large amount of valuable metals are not fully utilized, and the current discharge situation of the arsenic-containing waste is far from the requirement of the environmental protection department. As arsenic-containing wastes are mostly treated by a stockpiling and storing method for a long time, the harmless treatment of the arsenic-containing wastes becomes a problem to be solved as the high-concentration arsenic-containing wastes are accumulated more and more.
The arsenic-containing waste mainly comes from smelting waste residues, sediment obtained by treating arsenic-containing waste water and waste acid, arsenic-containing waste in the electronic industry, arsenic-containing anode mud generated in the electrolytic process and the like. At present, the method for treating the arsenic-containing waste at home and abroad mainly comprises a solidification method, a pyrogenic roasting method, a wet leaching method and other recovery methods, and has the disadvantages of harsh treatment conditions, high pollution and energy consumption and limited arsenic extraction rate. In recent years, more attention has been paid to a wet arsenic recovery technique in which arsenic-containing waste is recycled as a secondary resource.
CN102249609A discloses an arsenic-containing waste residue solidified body and a preparation method thereof, wherein the arsenic-containing waste residue is processed and then matched with industrial waste residue and mineral excitation materials to form a solidified body with high strength and arsenic leaching rate, and the arsenic residue is fixed, so that the solidified body is safe and reliable.
CN102247964A discloses a harmless treatment process for arsenic-containing waste dangerous chemicals, which comprises oxidizing arsenic-containing waste, forming arsenic-iron complex by ferric hydroxide, precipitating arsenic, and mixing with cement for solidification, thereby achieving the national relevant harmless standard.
CN 104357668A discloses a method for recovering valuable metals from arsenic-containing soot, comprising: (1) mixing the waste acid and the white ash, controlling the pH value to be 2.5-3.0, carrying out acid leaching at the temperature of 70-80 ℃, and filtering to obtain a leaching solution and lead slag; (2) replacing indium in the leachate by using zinc powder, and filtering to obtain indium slag; (3) and sequentially performing rotational flow electrodeposition dearsenification and dezincification on the filtrate to obtain arsenic slag and zinc slag.
However, none of the above methods can utilize valuable metal resources such as arsenic contained in arsenic-containing waste residues.
CN105384224A discloses a method and a device for degrading organic wastewater by using active oxygen generated by electrocatalysis reduction of air oxygen: air is continuously introduced into the cathode in the electrochemical reactor (aeration), and under the combined action of various catalysts and cathode current, a great amount of O is generated through a synergistic reaction3OH, H, free radical2O2And the active oxygen has extremely strong oxidizing capability, so that organic matters in the wastewater are directly oxidized and degraded, and the aim of deeply removing organic pollutants is fulfilled. The cathode used in the method is a reticular basket or frame made of insoluble metal, large granular active carbon and an oxygen reduction catalyst are filled in the reticular basket or frame, the filling method is that the active carbon and the oxygen reduction catalyst particles are mixed or the active carbon and the oxygen reduction catalyst are arranged in layers or the oxygen reduction catalyst is loaded on the active carbon through chemical reaction, a carbon rod or a metal wire is led out from the middle of the cathode active carbon and connected to a power supply cathode, the oxygen reduction catalyst consists of one or more main catalysts and auxiliary catalysts, the main catalysts are transition metals or mixtures of the transition metals and oxides thereof, the auxiliary catalysts are nonmetal simple substances or oxides or salts thereof, and the oxygen reduction catalyst has the functions of: making the air oxygen side surface adsorbed to the surface of cathode active carbon and reduced into micro active oxygen; the volume of the cathode active carbon is 10-30% of the effective volume of the electrochemical reactor device, and the nonmetal is any one or more of oxygen, nitrogen, phosphorus, sulfur and boron. However, said method is only suitable for treating organic contaminants present in the liquid phase and it requires the use of specific agentsThe catalyst and the auxiliary catalyst are not suitable for treating toxic solid wastes, so the application range is narrow. In addition, it does not disclose that the method can be used to treat arsenic-containing soot.
The white soot is obtained by collecting dust from flue gas in the metal smelting process, is one of the most representative alkaline wastes in the industry at present, contains valuable heavy metals such As Pb, Bi, Zn and the like, and harmful elements such As As and the like, and is not treated in time, so that not only can serious environmental pollution be caused, but also resource waste is caused. The existing common treatment method is to directly return the soot to the smelting system for treatment; the method not only reduces the processing capacity of the flash furnace and deteriorates the furnace condition, but also increases harmful components such As As in the furnace charge.
Therefore, there is a need in the art to develop a new method for treating arsenic-containing soot, which results in low energy consumption, high arsenic extraction rate, no pollution, mild process conditions, and little corrosion to equipment.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the electrochemical treatment method of the arsenic-containing soot, which has the advantages of high arsenic extraction rate, no pollution, mild process conditions, low cost and low requirement on equipment.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for electrochemically treating arsenic-containing soot, comprising the steps of:
(1) mixing alkali, a solvent and arsenic-containing soot, or mixing an alkali solution and arsenic-containing soot to obtain a mixture;
(2) placing the mixture serving as an electrolyte in an electrochemical reaction device for carrying out electrochemical reaction, wherein oxidizing gas is introduced into the electrolyte in the electrochemical reaction process;
(3) and (3) carrying out solid-liquid separation on the reaction product obtained in the step (2) to obtain an arsenic-containing solution.
The electrochemical treatment method of the arsenic-containing soot utilizes the coupling effect of the anode electrochemical direct oxidation and the catalytic oxidation of the cathode to generate active oxygen (the catalytic oxidation reaction is generated on the surface of an electrode and is a catalytic reaction generated when the active oxygen is generated on the surface of the electrode, and the active oxygen is generated by the oxidizing gas), the reaction reduces the reaction temperature and the concentration of a reaction medium, namely alkali solution, and realizes the high-efficiency oxidative decomposition of an arsenic-containing phase in the arsenic-containing waste under mild conditions and the high-efficiency extraction of arsenic.
The electrochemical reaction process comprises the following chemical reactions:
O2+H2O+2e-→HO2 -+OH-(1)
As3++HO2 -→As5++OH-(2)
the alkali solution in the step (1) can be prepared from alkali and a solvent. In step (1), the arsenic-containing soot may be directly mixed with an alkali solution or may be mixed with a separate alkali and solvent.
The arsenic-containing soot in step (1) is selected from any one or a combination of at least two of copper converter white soot, copper smelting flash furnace soot, high arsenic tin smelting soot or arsenic zinc smelting soot, and typical but non-limiting combinations include copper converter white soot and copper smelting flash furnace soot, high arsenic tin smelting soot and arsenic zinc smelting soot, copper converter white soot, copper smelting flash furnace soot and high arsenic tin smelting soot. The exemplary arsenic-containing soot is typically arsenic-containing soot, which may also be other arsenic-containing soot, not to mention here.
Preferably, the arsenic-containing soot of step (1) is pretreated and then mixed with an alkali and a solvent or an alkali solution.
Preferably, the pre-treatment comprises mechanical activation and/or high temperature roasting at a temperature of 700 ℃ to 800 ℃, such as 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 780 ℃, 790 ℃ or the like.
Preferably, the mechanical activation comprises ball milling the arsenic-containing soot for 20-60 min, such as 25min, 30min, 40min, 50min or 55 min. The ball milling may be carried out in a ball mill.
The concentration of the alkali in the mixed solution of the alkali and the solvent or the alkali solution in the step (1) is 0.01-10M, such as 0.03M, 0.05M, 0.08M, 0.1M, 0.3M, 0.5M, 0.8M, 1M, 1.5M, 2M, 2.5M, 3M, 3.5M, 4M, 4.5M, 5M, 5.5M, 6M, 7M, 8M or 9M.
Preferably, the alkali solution in step (1) is selected from sodium hydroxide solution and/or potassium hydroxide solution; the alkali is selected from sodium hydroxide and/or potassium hydroxide.
The solid-to-liquid ratio of the mixed solution or the alkaline solution formed by the arsenic-containing soot, the alkali and the solvent in the step (1) is 0.1-100 g/L, such as 0.3g/L, 0.5g/L, 0.8g/L, 1g/L, 2g/L, 5g/L, 8g/L, 10g/L, 15g/L, 20g/L, 30g/L, 40g/L, 50g/L, 60g/L, 70g/L, 80g/L or 90 g/L. Under the condition of the solid-liquid ratio, the method has high arsenic extraction rate and good economical efficiency.
The electrochemical reaction device in the step (2) comprises an electrolytic bath, a working electrode and a counter electrode.
Preferably, the electrolytic cell is an atmospheric electrolytic cell, i.e. the electrolytic cell can be used at a standard atmospheric pressure.
Preferably, the working electrode is selected from carbon material electrodes and the counter electrode is selected from graphite electrodes or inert electrodes.
Preferably, the working electrode is selected from a graphite rod, a graphite plate, a carbon felt electrode or a carbon fiber electrode.
Preferably, the counter electrode is selected from a graphite rod, a graphite plate or a platinum electrode.
Preferably, the morphology of the working electrode and the counter electrode is independently selected from rod-like or plate-like.
Preferably, the electrochemical reaction device further comprises a reference electrode selected from a saturated calomel electrode or a mercury/mercury oxide electrode. The electrochemical catalytic oxidation reaction using the three-electrode system is beneficial to knowing the reaction state in the electrolytic cell in real time so as to adjust the electrolyte or the voltage.
The electrochemical reaction in the step (2) is carried out at 20-140 deg.C, such as 25 deg.C, 30 deg.C, 40 deg.C, 50 deg.C, 55 deg.C, 65 deg.C, 75 deg.C, 85 deg.C, 95 deg.C, 100 deg.C, 105 deg.C, 110 deg.C, 120 deg.C, 130 deg.C or 140 deg.C, preferably 20-100 deg.C. The reaction can be carried out at normal temperature, so that the energy consumption is greatly reduced.
Preferably, the time of the electrochemical reaction in the step (2) is more than 1h, such as 1.5h, 2.5h, 3h, 4h, 5h, 7h, 8h or 10h, and the like, and preferably 2 to 6 h. The reaction time is longer than 1h, and the arsenic dissolution rate can be rapidly improved.
The electrochemical reaction in the step (2) is carried out under the condition that the voltage is more than-0.4V, such as-0.6V, -0.8V, -1.0V, -1.2V, -1.5V, -2V, -3V, -4V or-5V, and the like, and the voltage is preferably-0.4 to-5V. The negative sign represents the cathodic potential and does not indicate magnitude. The voltage of the electrolytic cell provides a driving force, the reaction can not be started when the voltage is lower than 0.4V, and the reaction can be started when the voltage is higher than 0.4V, so that the cell voltage is increased, and the reaction rate can be increased.
The electrochemical reaction in the step (2) is carried out under the stirring condition, and the stirring speed is 800-2100 rpm, such as 800rpm, 850rpm, 900rpm, 950rpm, 1000rpm, 1100rpm, 1200rpm, 1300rpm, 1400rpm, 1500rpm, 1600rpm, 1800rpm or 2000rpm, and the like, preferably 1000-1500 rpm. The stirring is beneficial to the uniformity of the electrolyte in the electrolytic bath and is more beneficial to the reaction.
The oxidizing gas in the step (2) is selected from any one of air, oxygen or oxygen-enriched air or a combination of at least two of the air and the oxygen, and oxygen is preferred. The oxygen-enriched air refers to air with the oxygen content of 90-96% by volume. The combination of oxidizing gases may be a combination of air and oxygen, a combination of oxygen and oxygen-enriched air, a combination of air, oxygen and oxygen-enriched air. The oxidizing gas has an oxidizing effect on the arsenic-containing waste residue, and the oxidizing gas generates active oxygen species in an electrochemical reaction, so that the oxidizing gas can be used for oxidizing the arsenic-containing waste residue.
Preferably, the flow rate of the oxidizing gas introduced in step (2) is 100mL/min or more, for example, 200mL/min, 400mL/min, 600mL/min, 800mL/min, 900mL/min, or 1L/min, and the flow rate is preferably 400mL/min or more. The reaction effect is poor when the flow rate of the oxidizing gas is low; therefore, the flow rate of the oxidizing gas is preferably 100mL/min or more, but too high a flow rate causes the inside of the electrolytic cell to fluctuate too much, and thus the elution of arsenic is not facilitated.
As a preferable technical solution, the electrochemical treatment method of the arsenic-containing soot comprises the following steps:
(1) mixing an alkali and a solvent with the arsenic-containing soot, or mixing an alkali solution with the arsenic-containing soot to obtain a mixture; wherein the concentration of alkali in the mixed solution or alkali solution formed by the alkali and the solvent is 0.01-10M, and the solid-to-liquid ratio of the arsenic-containing soot to the mixed solution or alkali solution formed by the alkali and the solvent is 0.1-100 g/L;
(2) placing the mixture as an electrolyte in an electrochemical reaction device, carrying out electrochemical reaction at the temperature of 20-140 ℃, the stirring speed of 800-2100 rpm and the voltage of more than-0.4V, and introducing oxidizing gas with the flow rate of more than 100mL/min into the mixture in the electrochemical reaction process; wherein the time of the electrochemical reaction is more than 1 h;
(3) and (3) carrying out solid-liquid separation on the reaction product obtained in the step (2) to obtain an arsenic-containing solution.
The solid-liquid separation in the present invention is a conventional operation in the art, and a typical but non-limiting solid-liquid separation method may be centrifugation or filtration.
The data ranges recited in the present invention include not only the point values of the illustrated sentences, but also any point values within the data ranges not illustrated, which are not exhaustive for reasons of space and brevity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the electrochemical treatment method of the arsenic-containing soot provided by the invention adopts normal pressure operation, the reaction temperature is low (the reaction temperature is only 20-140 ℃), and the reaction temperature is reduced compared with the traditional process (the temperature range adopted when the arsenic-containing soot is dissolved out by a high-temperature and high-pressure alkali medium is 140-;
(2) according to the electrochemical treatment method of the arsenic-containing soot, provided by the invention, impurities are not introduced into a system from a reaction medium, so that the subsequent separation is facilitated; the concentration of the used alkali is greatly reduced (the concentration of the alkali solution can be as low as 0.01M), and the alkali consumption is reduced;
(3) the electrochemical treatment method of the arsenic-containing soot provided by the invention utilizes a method of coupling direct anode oxidation and cathode active oxygen catalytic oxidation, thereby promoting the oxidation efficiency and improving the recovery rate of arsenic (which can be improved by 30-50%);
(4) in the electrochemical treatment method for the arsenic-containing soot, no auxiliary material is added in the treatment process, and compared with the traditional process, the slag discharge amount can be reduced by 30-50 wt%;
(5) the electrochemical reaction operation automation degree of the electrochemical treatment method of the arsenic-containing soot provided by the invention is high, the human input can be reduced, good economic benefit and social benefit can be brought, and the method has a good application prospect.
Drawings
FIG. 1 is a flow chart of a process for treating arsenic-containing soot according to one embodiment of the present invention.
FIG. 2 is a graph showing the arsenic leaching rate provided in example 1.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
FIG. 1 is a flow chart of a process for treating arsenic-containing soot, according to an embodiment of the present invention, wherein the electrochemical treatment method of the arsenic-containing soot comprises the following steps:
(1) mixing the arsenic-containing soot with an alkaline solution (or a solvent and an alkali) to obtain a mixture;
(2) placing the mixture as an electrolyte in an electrochemical reaction device for carrying out electrochemical catalytic oxidation reaction, wherein oxidizing gas is introduced into the electrolyte in the electrochemical reaction process;
(3) and (3) carrying out solid-liquid separation on the reaction product obtained in the step (2) to obtain an arsenic-containing solution.
Example 1
The electrochemical treatment method of the arsenic-containing soot which is the white soot of the copper converter comprises the following steps:
(1) preparing materials: mixing the arsenic-containing soot which is sieved into 80 meshes with a potassium hydroxide aqueous solution to prepare an electrolyte, and preheating to 60 ℃, wherein the content of potassium hydroxide in the potassium hydroxide solution is 1M, and the liquid-solid ratio of the arsenic-containing soot to the potassium hydroxide solution is 1 g/L;
(2) electrochemical reaction: adding the raw material electrolyte obtained in the step (1) into a normal-pressure electrolytic tank, introducing oxygen into the electrolyte, wherein the oxygen flow is 400mL/min, the mechanical stirring speed is 800rpm, a carbon felt electrode is taken as a working electrode, a carbon rod is taken as a counter electrode, a mercury/mercury oxide electrode is taken as a reference electrode, the control potential is-1V, the electrochemical reaction time is 4h, and the electrochemical reaction temperature is 60 ℃;
(3) solid-liquid separation: and (3) filtering and separating the solid-liquid mixture obtained by the electrochemical reaction in the step (2) to obtain an arsenic-containing solution, diluting the solution, testing the arsenic content of the solution by using an ICP (inductively coupled plasma) or titration method, and calculating to obtain the arsenic dissolution rate of 91.8% (shown in figure 2).
Example 2
The electrochemical treatment method of the arsenic-containing soot which is the white soot of the copper converter comprises the following steps:
(1) mixing the arsenic-containing soot with a sodium hydroxide solution with the concentration of 0.01M, wherein the solid-to-liquid ratio of the arsenic-containing soot to the sodium hydroxide solution is 0.1g/L, so as to obtain a mixture;
(2) placing the mixture as electrolyte in an electrolytic cell, performing electrochemical catalytic oxidation reaction at 20 ℃ and at a stirring speed of 2100rpm, and introducing oxygen-enriched air into the mixture in the electrochemical catalytic oxidation process; wherein the time of the electrochemical catalytic oxidation reaction is 2h, the voltage of the electrolytic cell is-0.4V, and the flow of the introduced oxygen-enriched air is 100 mL/min; the electrolytic cell takes a graphite rod as a working electrode, a platinum electrode as a counter electrode and a mercury/mercury oxide electrode as a reference electrode;
(3) and (3) carrying out solid-liquid separation on the reaction product obtained in the step (2) to obtain an arsenic-containing solution, testing the arsenic content in the arsenic-containing solution by using an ICP (inductively coupled plasma) or titration method after dilution, and calculating to obtain the arsenic dissolution rate of 87%.
Example 3
The electrochemical treatment method of the arsenic-containing soot which is the white soot of the copper converter comprises the following steps:
(1) mixing arsenic-containing soot with an alkaline solution with the concentration of 10M, wherein the solid-to-liquid ratio of the arsenic-containing soot to the alkaline solution is 100g/L, so as to obtain a mixture;
(2) placing the mixture as electrolyte in an electrolytic cell, performing electrochemical catalytic oxidation reaction at 140 ℃ and at a stirring speed of 800rpm, and introducing air into the mixture in the electrochemical catalytic oxidation process; wherein the time of the electrochemical catalytic oxidation reaction is 1h, the voltage of the electrolytic cell is-5.0V, and the flow of the introduced air is 500 mL/min; the electrolytic cell takes a graphite plate as a working electrode, takes the graphite plate as a counter electrode and takes a mercury/mercury oxide electrode as a reference electrode;
(3) and (3) carrying out solid-liquid separation on the reaction product obtained in the step (2) to obtain an arsenic-containing solution, testing the arsenic content in the arsenic-containing solution by using an ICP (inductively coupled plasma) or titration method after dilution, and calculating to obtain the arsenic dissolution rate of 89%.
Example 4
The electrochemical treatment method of the arsenic-containing soot which is the white soot of the copper converter comprises the following steps:
(1) mixing arsenic-containing soot with an alkaline solution with the concentration of 5M, wherein the solid-to-liquid ratio of the arsenic-containing soot to the alkaline solution is 50g/L, so as to obtain a mixture;
(2) placing the mixture as electrolyte in an electrolytic cell, performing electrochemical catalytic oxidation reaction at 50 ℃ and at a stirring speed of 1500rpm, and introducing oxygen into the mixture in the electrochemical catalytic oxidation process; wherein the time of the electrochemical catalytic oxidation reaction is 2h, the voltage of the electrolytic cell is-0.4V, and the flow of the introduced oxygen is 400 mL/min; the electrolytic cell takes a carbon fiber electrode as a working electrode, a graphite plate as a counter electrode and a mercury/mercury oxide electrode as a reference electrode;
(3) and (3) carrying out solid-liquid separation on the reaction product obtained in the step (2) to obtain an arsenic-containing solution, testing the arsenic content in the arsenic-containing solution by using an ICP (inductively coupled plasma) or titration method after dilution, and calculating to obtain the arsenic dissolution rate of 94%.
Example 5
The electrochemical treatment method of the arsenic-containing soot which is the white soot of the copper converter comprises the following steps:
(1) mixing arsenic-containing soot with an alkaline solution with the concentration of 6M, wherein the solid-to-liquid ratio of the arsenic-containing soot to the alkaline solution is 60g/L, so as to obtain a mixture;
(2) placing the mixture as electrolyte in an electrolytic cell, carrying out electrochemical catalytic oxidation reaction at 100 ℃ and at a stirring speed of 1000rpm, and introducing oxygen into the mixture in the electrochemical catalytic oxidation process; wherein the time of the electrochemical catalytic oxidation reaction is 6h, the voltage of the electrolytic cell is-5.0V, and the flow of the introduced oxygen is 600 mL/min; the electrolytic cell takes a carbon fiber electrode as a working electrode, a graphite rod as a counter electrode and a mercury/mercury oxide electrode as a reference electrode;
(3) and (3) carrying out solid-liquid separation on the reaction product obtained in the step (2) to obtain an arsenic-containing solution, testing the arsenic content in the arsenic-containing solution by using an ICP (inductively coupled plasma) or titration method after dilution, and calculating to obtain the arsenic dissolution rate of 93.5%.
Example 6
Except that the 1M potassium hydroxide solution in the step (1) is replaced by 0.1M sodium hydroxide solution; the temperature of the electrochemical reaction in the step (2) was the same as that in example 1 except that the temperature was 20 ℃.
After the obtained arsenic-containing solution is diluted, the content of arsenic in the solution is tested by an ICP (inductively coupled plasma) or titration method, and the dissolution rate of arsenic is calculated to be 75%.
Example 7
Except that the 1M potassium hydroxide solution in the step (1) is replaced by 0.1M sodium hydroxide solution; the temperature of the electrochemical reaction in the step (2) was the same as that in example 1 except that the temperature was 40 ℃.
After the obtained arsenic-containing solution is diluted, the content of arsenic in the solution is tested by an ICP (inductively coupled plasma) or titration method, and the dissolution rate of arsenic is calculated to be 83%.
Example 8
Except that the 1M potassium hydroxide solution in the step (1) is replaced by 0.1M sodium hydroxide solution; the temperature of the electrochemical reaction in the step (2) was the same as that in example 1 except that the temperature was 60 ℃.
After the obtained arsenic-containing solution is diluted, the content of arsenic in the solution is tested by an ICP (inductively coupled plasma) or titration method, and the dissolution rate of arsenic is calculated to be 88%.
Example 9
Except that the 1M potassium hydroxide solution in the step (1) is replaced by 0.1M sodium hydroxide solution; the temperature of the electrochemical reaction in the step (2) was the same as that in example 1 except that the temperature was 80 ℃.
After the obtained arsenic-containing solution is diluted, the content of arsenic in the solution is tested by an ICP (inductively coupled plasma) or titration method, and the dissolution rate of arsenic is calculated to be 91%.
Example 10
Except that 1M potassium hydroxide solution in the step (1) is replaced by 1M sodium hydroxide solution; the temperature of the electrochemical reaction in the step (2) was the same as that in example 1 except that the temperature was 20 ℃.
After the obtained arsenic-containing solution is diluted, the content of arsenic in the solution is tested by an ICP (inductively coupled plasma) or titration method, and the dissolution rate of arsenic is calculated to be 92%.
Example 11
The procedure of example 1 was repeated, except that the stirring speed in step (2) was changed to 700 rpm.
After the obtained arsenic-containing solution is diluted, the content of arsenic in the solution is tested by an ICP (inductively coupled plasma) or titration method, and the dissolution rate of arsenic is calculated to be 87%.
Example 12
The procedure was as in example 1 except that the stirring speed in step (2) was changed to 1400 rpm.
After the obtained arsenic-containing solution is diluted, the content of arsenic in the solution is tested by an ICP (inductively coupled plasma) or titration method, and the dissolution rate of arsenic is calculated to be 91.5%.
Example 13
The procedure was as in example 1 except that the stirring speed in step (2) was changed to 2100 rpm.
After the obtained arsenic-containing solution is diluted, the content of arsenic in the solution is tested by an ICP (inductively coupled plasma) or titration method, and the dissolution rate of arsenic is calculated to be 92.5%.
Example 14
The procedure was as in example 1, except that the cell in step (2) did not contain a reference electrode.
After the obtained arsenic-containing solution is diluted, the content of arsenic in the solution is tested by an ICP (inductively coupled plasma) or titration method, and the dissolution rate of arsenic is calculated to be 88%. Therefore, compared with a two-electrode system, the three-electrode system can control the oxidation potential more accurately and monitor the potential fluctuation in real time, so that the arsenic dissolution rate is higher.
Example 15
The procedure of example 1 was repeated, except that the stirring was not carried out during the electrochemical reaction in step (2).
After the obtained arsenic-containing solution is diluted, the content of arsenic in the solution is tested by an ICP (inductively coupled plasma) or titration method, and the dissolution rate of arsenic is calculated to be 78%.
The white ash of the copper converter in the embodiments 1 to 15 is replaced by any one of or the combination of at least two of the smoke dust of the copper smelting flash furnace, the smoke dust of the high arsenic tin smelting and the smoke dust of the arsenic zinc smelting, or replaced by other smoke dust containing arsenic, the obtained arsenic-containing solution is diluted and then the content of arsenic in the solution is tested by an ICP (inductively coupled plasma) or titration method, and the arsenic dissolution rate is calculated to be 80 to 93 percent. And the tendency of the magnitude of the arsenic dissolution rate in each example after the raw material replacement was the same as that in examples 1 to 15.
Comparative example 1
The procedure of example 1 was repeated except that the potassium hydroxide solution in step (1) was replaced with a nitric acid solution of the same concentration.
After the obtained arsenic-containing solution is diluted, the content of arsenic in the solution is tested by an ICP (inductively coupled plasma) or titration method, and the dissolution rate of arsenic is calculated to be 25%.
Comparative example 2
The procedure of example 1 was repeated, except that the electrolytic cell was not energized in the step (2).
After the obtained arsenic-containing solution is diluted, the content of arsenic in the solution is tested by an ICP (inductively coupled plasma) or titration method, and the dissolution rate of arsenic is calculated to be 30%.
Comparative example 3
The procedure of example 1 was repeated, except that no oxygen gas was introduced in the step (2).
After the obtained arsenic-containing solution is diluted, the content of arsenic in the solution is tested by an ICP (inductively coupled plasma) or titration method, and the dissolution rate of arsenic is calculated to be 53%.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (23)

1. The electrochemical treatment method of the arsenic-containing soot is characterized by comprising the following steps of:
(1) mixing alkali, a solvent and arsenic-containing soot, or mixing an alkali solution and arsenic-containing soot to obtain a mixture;
(2) placing the mixture serving as an electrolyte in an electrochemical reaction device for carrying out electrochemical reaction, wherein oxidizing gas is introduced into the electrolyte in the electrochemical reaction process;
(3) carrying out solid-liquid separation on the reaction product obtained in the step (2) to obtain an arsenic-containing solution;
pretreating the arsenic-containing soot in the step (1) and then mixing the pretreated arsenic-containing soot with alkali and a solvent or an alkali solution;
the pretreatment comprises mechanical activation and/or high-temperature roasting, the temperature of the high-temperature roasting is 700-800 ℃, and the mechanical activation comprises ball milling of arsenic-containing soot for 20-60 min;
the electrochemical reaction in the step (2) is carried out at the temperature of 20-140 ℃;
the arsenic-containing soot in the step (1) is selected from any one of or a combination of at least two of copper converter white soot, copper smelting flash furnace soot, high arsenic tin smelting soot or arsenic zinc-containing smelting soot.
2. The method for electrochemically treating arsenic-containing soot as claimed in claim 1, wherein the concentration of alkali in the mixed solution of alkali and solvent or the alkali solution in step (1) is 0.01-10M.
3. The method of claim 1, wherein the alkaline solution of step (1) is selected from a sodium hydroxide solution and/or a potassium hydroxide solution; the alkali is selected from sodium hydroxide and/or potassium hydroxide.
4. The method for electrochemically treating the arsenic-containing soot as claimed in claim 1, wherein the solid-to-liquid ratio of the arsenic-containing soot in step (1) to a mixed solution or an alkaline solution of an alkaline and a solvent is 0.1 to 100 g/L.
5. The method of claim 1, wherein the electrochemical reaction apparatus of step (2) comprises an electrolytic bath, a working electrode, and a counter electrode.
6. The method of claim 5, wherein the electrolytic cell is an atmospheric pressure electrolytic cell.
7. The method of claim 5, wherein the working electrode is selected from carbon material electrodes and the counter electrode is selected from graphite electrodes or inert electrodes.
8. The method of claim 7, wherein the working electrode is selected from the group consisting of a graphite rod, a graphite plate, a carbon felt electrode, and a carbon fiber electrode.
9. The method of claim 7, wherein the counter electrode is selected from the group consisting of a graphite rod, a graphite plate, and a platinum electrode.
10. The method of claim 7, wherein the working electrode and the counter electrode are in the form of rods or plates, independently.
11. The method of claim 5, wherein the electrochemical reaction device further comprises a reference electrode selected from a saturated calomel electrode or a mercury/mercury oxide electrode.
12. The method for electrochemically treating arsenic-containing soot as claimed in claim 1, wherein the electrochemical reaction in step (2) is carried out at 20 to 100 ℃.
13. The method of claim 1, wherein the electrochemical reaction of step (2) is carried out for a time period greater than 1 hour.
14. The method for electrochemically treating arsenic-containing soot as claimed in claim 13, wherein the time for the electrochemical reaction in step (2) is 2-6 hours.
15. The method of claim 1, wherein the electrochemical reaction in step (2) is carried out at a voltage of-0.4V or more.
16. The method of claim 15, wherein the electrochemical reaction in step (2) is carried out at a voltage of-0.4 to-5V.
17. The method for electrochemically treating arsenic-containing soot as claimed in claim 1, wherein the electrochemical reaction in step (2) is carried out under stirring at a rate of 800 to 2100 rpm.
18. The method for electrochemically treating arsenic-containing soot as claimed in claim 17, wherein the electrochemical reaction in step (2) is carried out under stirring at a rate of 1000 to 1500 rpm.
19. The method of claim 1, wherein the oxidizing gas in step (2) is selected from any one of air, oxygen, or oxygen-enriched air, or a combination of at least two thereof.
20. The method of claim 19, wherein the oxidizing gas of step (2) is selected from oxygen.
21. The method according to claim 1, wherein the oxidizing gas is introduced at a flow rate of 100mL/min or more in step (2).
22. The method of claim 21, wherein the oxidizing gas is introduced at a flow rate of 400mL/min or more in step (2).
23. The method of claim 1, wherein the method of electrochemically treating the arsenic-containing soot comprises the steps of:
(1) mixing an alkali and a solvent with the arsenic-containing soot, or mixing an alkali solution with the arsenic-containing soot to obtain a mixture; wherein the concentration of alkali in the mixed solution or alkali solution formed by the alkali and the solvent is 0.01-10M, and the solid-to-liquid ratio of the arsenic-containing soot to the mixed solution or alkali solution formed by the alkali and the solvent is 0.1-100 g/L;
(2) placing the mixture as an electrolyte in an electrochemical reaction device, carrying out electrochemical reaction at the temperature of 20-140 ℃, the stirring speed of 800-2100 rpm and the voltage of more than-0.4V, and introducing oxidizing gas with the flow rate of more than 100mL/min into the mixture in the electrochemical reaction process; wherein the time of the electrochemical reaction is more than 1 h;
(3) and (3) carrying out solid-liquid separation on the reaction product obtained in the step (2) to obtain an arsenic-containing solution.
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Publication number Priority date Publication date Assignee Title
CN1693492A (en) * 2005-05-13 2005-11-09 中南大学 Method of recovering gallium and arsenic from gallium arsenate industry waste material
CN102330108A (en) * 2011-08-27 2012-01-25 南昌航空大学 Method for treating sodium arsenate composite salt solution in antimony smelting arsenic alkaline residue
CN103922446A (en) * 2014-04-25 2014-07-16 中国地质大学（武汉） Electrochemical oxidation method for trivalent arsenic in underground water
CN105039721A (en) * 2015-06-19 2015-11-11 金川集团股份有限公司 Arsenic open-circuit processing operation method for arsenious material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1693492A (en) * 2005-05-13 2005-11-09 中南大学 Method of recovering gallium and arsenic from gallium arsenate industry waste material
CN102330108A (en) * 2011-08-27 2012-01-25 南昌航空大学 Method for treating sodium arsenate composite salt solution in antimony smelting arsenic alkaline residue
CN103922446A (en) * 2014-04-25 2014-07-16 中国地质大学（武汉） Electrochemical oxidation method for trivalent arsenic in underground water
CN105039721A (en) * 2015-06-19 2015-11-11 金川集团股份有限公司 Arsenic open-circuit processing operation method for arsenious material

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