CN113289306A - Treatment method of waste residue containing arsenic sulfide - Google Patents
Treatment method of waste residue containing arsenic sulfide Download PDFInfo
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Abstract
The invention provides a method for treating waste residue containing arsenic sulfide. The method comprises the following steps: adding an oxidant into the arsenic sulfide-containing waste residue to enable arsenic sulfide in the arsenic sulfide-containing waste residue to be subjected to oxidation reaction to form sulfur and arsenic oxide, and further obtaining reaction residue; mixing the reaction residue with a flotation agent, and performing flotation separation to obtain sulfur and residual slurry; a stabilizing agent is added to the remaining slurry to stabilize the arsenic ions therein. The method for treating the arsenic sulfide-containing waste residue can carry out harmless stabilization treatment on the arsenic sulfide-containing waste residue more efficiently, can realize recycling of sulfur more efficiently in the treatment process, has the advantages of simpler process, easier realization, lower treatment environment requirement, large-scale and large-batch treatment, higher arsenic fixation rate, stable quality of products after stabilization, no possibility of secondary pollution, smaller capacity-increasing ratio and smaller pressure for reservoir capacity limitation of landfill plants.
Description
Technical Field
The invention relates to treatment of arsenic-containing waste residues, in particular to a treatment method of arsenic sulfide-containing waste residues.
Background
Arsenic can enter human bodies through respiratory tracts, skins and digestive tracts to form a series of highly toxic compounds which are absorbed by the human bodies, thereby causing neurasthenia syndrome, polyneuropathy, skin mucosa pathological changes and the like. Also, arsenic compounds, which are protoplasmic toxicants having metalloid properties and have a wide range of biological effects, have been identified as the first carcinogen by the united states Centers for Disease Control (CDC) and the international agency for research on cancer (IARC). The arsenic sulfide-containing waste residue is mainly from waste residue generated in the treatment process of smelting waste acid, generally comprises 35 wt% -70 wt% of arsenic sulfide (main component), and also comprises one or more of copper sulfide, lead sulfide, iron sulfide and nickel sulfide. The waste residue containing arsenic sulfide has high toxicity, high pollution and high permeability, and is easy to generate secondary pollution due to improper treatment, thereby causing great harm to the environment. Arsenic sulfide-containing waste residues are mostly treated by a stockpiling and storing method for a long time, and the more high-concentration arsenic sulfide-containing waste residues are accumulated, the more serious the arsenic sulfide-containing waste residues pollute the environment, and further the human health is damaged. Therefore, the harmless treatment of the arsenic sulfide-containing waste slag becomes a problem to be solved urgently.
At present, two main harmless stabilization treatment modes aiming at arsenic sulfide-containing waste residues are provided: one is that arsenic sulfide-containing waste residue can be treated by adding a medicament to reach the standard of landfill in the field, but the addition amount is large (more than 200%), enterprises or hazardous waste treatment centers cannot accept the cost, and in addition, the storage capacity of the landfill is limited, so the service life of the landfill is greatly shortened. The other is to perform resource utilization on heavy metals (such as arsenic) and harmful elements (such as sulfur) in the arsenic sulfide-containing waste residue, but due to the implementation of national policies, arsenic is prohibited to be used in the pesticide and glass industry, except that a small amount of arsenic in the arsenic sulfide-containing waste residue is purified to be an arsenic simple substance and then processed into a gallium arsenide semiconductor material, but the market consumption of the gallium arsenide semiconductor material is low at present, and large-area resource utilization of arsenic cannot be realized.
CN110404227A discloses a reduction solidification stabilization method of arsenic sulfide slag, which realizes the solidification stabilization of arsenic sulfide slag by introducing a mineralizer stannous chloride, and adjusting the concentration of the mineralizer, the solid-to-liquid ratio of the arsenic sulfide slag, the pH value of a solution, the hydrothermal temperature and the like. However, the hydrothermal method adopted for the treatment has high requirements on the treatment environment, and meanwhile, the hydrothermal method cannot be applied to industrial production in a large scale. CN105967232A discloses a method for leaching and synchronously stabilizing arsenic sulfide slag, which converts arsenic in high-arsenic sulfide slag into scorodite crystals to achieve harmless treatment of arsenic slag, but the treatment conditions are strict, the arsenic slag is only allowed to be carried out in a strong acid environment, and meanwhile, the temperature is also higher, the preparation process is complex, and the addition amount of a stabilizing agent is larger.
In a word, aiming at the treatment method of the arsenic sulfide-containing waste residue, the addition amount of the stabilizing agent is large when arsenic is stabilized, so that enterprises or hazardous waste treatment centers cannot accept the high cost. Meanwhile, the waste residue containing arsenic sulfide also contains sulfur element, the existing treatment method does not explain about the recovery of sulfur, and the resource utilization rate of sulfur is low.
Disclosure of Invention
The invention mainly aims to provide a method for treating waste residues containing arsenic sulfide, which aims to solve the problems that in the prior art, the addition amount of a stabilizing agent is large when the waste residues containing arsenic sulfide are treated, and sulfur is not effectively recovered.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for treating arsenic sulfide-containing waste slag. The method comprises the following steps: adding an oxidant into the arsenic sulfide-containing waste residue to enable arsenic sulfide in the arsenic sulfide-containing waste residue to be subjected to oxidation reaction to form sulfur and arsenic oxide, and further obtaining reaction residue; mixing the reaction residue with a flotation agent, and performing flotation separation to obtain sulfur and residual slurry; a stabilizing agent is added to the remaining slurry to stabilize the arsenic ions therein.
Further, the oxidant is selected from one or more of liquid oxidant, chlorate, hypochlorite. Preferably, the liquid oxidant is selected from hydrogen peroxide. Preferably, the chlorate is selected from one or more of sodium chlorate, calcium chlorate, potassium chlorate and sodium perchlorate. Preferably, the hypochlorite is selected from one or more of calcium hypochlorite, sodium hypochlorite, hypochlorous acid, potassium hypochlorite. More preferably, the oxidant is hydrogen peroxide, or a mixture of sodium chlorate and calcium chlorate in a weight ratio of (1-2): 1, or a mixture of calcium hypochlorite and sodium hypochlorite in a weight ratio of (1-1.5): 1, or a mixture of sodium chlorate, sodium hypochlorite and hydrogen peroxide in a weight ratio of (1-1.5): 1.
Furthermore, the amount of the oxidant is 25 to 60 percent of the weight of the arsenic sulfide-containing waste residue.
Furthermore, the amount of the oxidant is 35 to 45 percent of the weight of the arsenic sulfide-containing waste residue.
Further, the stabilizing agent comprises a stabilizing agent, and the stabilizing agent is selected from one or more of aminocarboxylic acid chelating agent, organic multi-phosphoric acid chelating agent, sulfydryl-containing chelating agent and natural modified polymer trapping agent.
Further, the aminocarboxylic acid chelating agent is selected from one or more of ethylenediamine tetraacetic acid, aminotriacetic acid, diethylenetriamine pentaacetic acid, ethylenediamine tetraacetate, aminotriacetic acid salt and diethylenetriamine pentaacetate. Preferably, the organic polyphosphate chelating agent is selected from one or more of hydroxyethylidene-1, 1-diphosphonic acid, aminotrimethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, triethylene tetramine hexamethylene phosphonic acid, bis (1, 6-hexylene) triamine pentamethylene phosphonic acid, and polyaminopolyether tetramethylene phosphonic acid. Preferably, the thiol-containing chelating agent is selected from the group consisting of dithiocarboxylated acrylamide, 2-hydroxymethyl-4-mercaptothiophenol sodium salt, dithiocarbamate or tetrathiobisoxoformic acid. Preferably, the natural modified polymer trapping agent is selected from one or more of starches, celluloses, plant gums and polysaccharides.
Further, the stabilizing agent also comprises a curing agent, and the curing agent is selected from one or more of cement, fly ash and sodium silicate. Preferably, the weight ratio of the stabilizer to the curing agent is 1: 1-5. More preferably, the stabilizer is hydroxyethylidene-1, 1-diphosphonic acid and tetrathiobisoxyformic acid, the curing agent is cement, and the weight ratio of the hydroxyethylidene-1, 1-diphosphonic acid to the tetrathiobisoxyformic acid to the cement is (4-6): (4-6): 2; or the stabilizer is 2-hydroxymethyl-4-mercapto thiophenol sodium salt and polysaccharide, the curing agent is cement, and the weight ratio of the 2-hydroxymethyl-4-mercapto thiophenol sodium salt to the polysaccharide to the cement is (6-8): 2-4): 2.
Furthermore, the dosage of the stabilizing agent is 20 to 80 percent of the weight of the arsenic sulfide-containing waste residue. Preferably, the dosage of the stabilizing agent is 40 to 60 percent of the weight of the arsenic sulfide-containing waste residue.
Further, the flotation agent is one or a mixture of more of pine oil, camphor oil, methyl phenolic acid, C6-C8 fatty alcohol and alcohol ether. Preferably, the C6-C8 fatty alcohol is methyl isobutyl carbinol. Preferably, the alcohol ether is selected from propylene glycol ether and/or propylene glycol monoalkyl ether.
Furthermore, the amount of the flotation agent is 5-50% of the weight of the arsenic sulfide-containing waste residue. Preferably, the amount of the flotation agent is 15-30% of the weight of the arsenic sulfide-containing waste residue.
The method for treating the arsenic sulfide-containing waste residue can carry out harmless stabilization treatment on the arsenic sulfide-containing waste residue more efficiently, can realize recycling of sulfur more efficiently in the treatment process, has the advantages of simpler process, easier realization, lower treatment environment requirement, large-scale and large-batch treatment, higher arsenic fixation rate, stable quality of products after stabilization, no possibility of secondary pollution, smaller capacity-increasing ratio and smaller pressure for reservoir capacity limitation of landfill plants.
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The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic flow diagram illustrating a method for treating arsenic sulfide-containing waste slag according to an embodiment of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As described in the background section, the prior art treatment of arsenic sulfide-containing waste residues has large addition of stabilizing agents and does not provide effective recovery of sulfur.
In order to solve the problem, the invention provides a method for treating arsenic sulfide-containing waste slag, which comprises the following steps as shown in figure 1: adding an oxidant into the arsenic sulfide-containing waste residue to enable arsenic sulfide in the arsenic sulfide-containing waste residue to be subjected to oxidation reaction to form sulfur and arsenic oxide, and further obtaining reaction residue; mixing the reaction residue with a flotation agent, and performing flotation separation to obtain sulfur and residual slurry; a stabilizing agent is added to the remaining slurry to stabilize the arsenic ions therein.
According to the invention, arsenic sulfide is oxidized into sulfur and arsenic oxide by a pretreatment mode of firstly adding an oxidant, then the sulfur is obtained by flotation separation, and finally the arsenic oxide is stabilized. Based on the process, the invention more effectively separates arsenic and sulfur, improves the utilization rate of sulfur, and promotes better resource utilization effect of arsenic sulfide-containing waste residues because more scenes of resource utilization of sulfur are available. Meanwhile, as the procedures of oxidation and flotation separation of sulfur are carried out in the earlier stage, the subsequent residual slurry can achieve a good stabilizing effect on arsenic ions by only adding a relatively small amount of stabilizing agent, the possibility of secondary pollution is avoided, the capacity increase ratio is smaller (the capacity increase ratio is the ratio of the initial waste residue to the agent to increase the volume), and the pressure for limiting the storage capacity of a landfill plant is smaller.
In a word, the method for treating the waste residue containing arsenic sulfide can carry out harmless stabilization treatment on the waste residue containing arsenic sulfide more efficiently, can realize recycling of sulfur more efficiently in the treatment process, has simpler process, is easier to realize, has lower treatment environment requirement, can carry out large-scale mass treatment, has higher arsenic fixation rate, has stable quality of products after stabilization, has no possibility of secondary pollution, has smaller capacity-increasing ratio, and has lower pressure on reservoir capacity limitation of landfill plants.
Preferably, the oxidizing agent is selected from one or more of liquid oxidizing agents, chlorates, hypochlorites; preferably, the liquid oxidant is selected from hydrogen peroxide; preferably, the chlorate is selected from one or more of sodium chlorate, calcium chlorate, potassium chlorate and sodium perchlorate; preferably, the hypochlorite is selected from one or more of calcium hypochlorite, sodium hypochlorite, hypochlorous acid, potassium hypochlorite. When the oxidant is selected from the above types, the oxidation effect is better, more arsenic sulfide can be fully oxidized into sulfur, the recovery rate of the sulfur is higher, and meanwhile, the generated arsenic oxide and the sulfur are easier to separate in the subsequent flotation separation. Meanwhile, the oxidant of the type also has the advantages of mild reaction conditions, stable and easily controlled reaction system, no introduction of other impurities and the like. It should be noted that arsenic in arsenic sulfide slag exists in the form of trivalent arsenic ions, and it is inevitable that some of the trivalent arsenic ions are oxidized into pentavalent arsenic ions during the oxidation reaction. In order to reduce the possibility of oxidation of arsenic ions as much as possible, the oxidant is preferably hydrogen peroxide, or a mixture of sodium chlorate and calcium chlorate in a weight ratio of (1-2): 1, or a mixture of calcium hypochlorite and sodium hypochlorite in a weight ratio of (1-1.5): 1, or a mixture of sodium chlorate, sodium hypochlorite and hydrogen peroxide in a weight ratio of (1-1.5): 1. The hydrogen peroxide or the compound oxidant has better oxidation effect. In particular, in the oxidation process, sulfur ions can be oxidized into sulfur simple substances as much as possible, and trivalent arsenic ions can be reduced to be oxidized into arsenic ions with higher valence as much as possible. On one hand, the method is favorable for reducing the use amount of the oxidant, and on the other hand, the method is also favorable for promoting the subsequent stabilizing treatment of arsenic ions.
Based on the purposes of promoting the oxidizing agent to oxidize the arsenic sulfide better, leading the arsenic sulfide to be oxidized into sulfur more fully, leading the sulfur yield to be higher and avoiding excessive waste of reaction reagents, the use amount of the oxidizing agent is preferably 25 to 60 percent of the weight of the arsenic sulfide-containing waste residue. More preferably, the amount of the oxidant is 35-45% of the weight of the arsenic sulfide-containing waste residue.
Preferably, the stabilizing agent comprises a stabilizer selected from one or more of aminocarboxylic acid chelating agents, organic polyphosphonic acid chelating agents, sulfhydryl-containing chelating agents and natural modified polymer trapping agents. The stabilizing agent is selected from the reagent types, arsenic ions are fixed through chelation, more arsenic ions can be fixed under the condition of less adding amount of the stabilizing agent, a more stable product is formed, the effect of stabilizing the arsenic ions is better, meanwhile, the cost is low, secondary pollution is avoided, the capacity increasing ratio is smaller, the pressure for limiting the storage capacity of a landfill plant is smaller, and the industrial application is easier.
In a preferred embodiment, the aminocarboxylic acid chelating agent is selected from one or more of ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetate, nitrilotriacetate, diethylenetriaminepentaacetate. Specifically, the edetate can be disodium edetate and tetrasodium edetate. Preferably, the organic polyphosphate chelating agent is selected from one or more of hydroxyethylidene-1, 1-diphosphonic acid, aminotrimethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, triethylene tetramine hexamethylene phosphonic acid, bis (1, 6-hexylene) triamine pentamethylene phosphonic acid, and polyaminopolyether tetramethylene phosphonic acid; preferably, the thiol-containing chelating agent is selected from the group consisting of dithiocarboxylated acrylamide, 2-hydroxymethyl-4-mercaptothiophenol sodium salt, dithiocarbamate, tetrathiobisoxoformic acid; preferably, the natural modified polymer trapping agent is selected from one or more of starches, celluloses, plant gums and polysaccharides.
In a preferred embodiment, the stabilizing agent further comprises a curing agent selected from one or more of cement, fly ash and sodium silicate, and the weight ratio of the stabilizing agent to the curing agent is preferably 1: 1-5. And a curing agent is further added on the basis of the stabilizer, so that the arsenic fixing effect is better. Particularly, the weight ratio of the stabilizer to the curing agent is controlled within the range, more arsenic ions are fixed under the condition of less adding amount of the stabilizer, the curing treatment effect is better, and the secondary pollution to the environment is avoided to a greater extent. More preferably, the stabilizer is hydroxyethylidene-1, 1-diphosphonic acid and tetrathiobisoxyformic acid, the curing agent is cement, and the weight ratio of the hydroxyethylidene-1, 1-diphosphonic acid to the tetrathiobisoxyformic acid to the cement is (4-6): (4-6): 2; alternatively, the stabilizer is 2-hydroxymethyl-4-mercaptothiophenol sodium salt and a polysaccharide, including but not limited to chitosan, dextran, and starch. The curing agent is cement, and the weight ratio of the 2-hydroxymethyl-4-mercapto thiophenol sodium salt to the polysaccharide to the cement is (6-8): 2-4): 2. By using the compound stabilizer and the curing agent, the arsenic ion curing effect is better while the addition amount of the stabilizer is reduced.
In order to stabilize arsenic with better effect, the stabilizing agent is preferably used in an amount of 20-80% by weight of the arsenic sulfide-containing waste residue. Within the range, the stabilized product has better stability, no secondary pollution, smaller compatibilization ratio, smaller pressure on reservoir capacity limitation of a landfill plant and better industrial application.
Preferably, the flotation agent is one or more of pine oil, camphor oil, methyl phenolic acid, C6-C8 fatty alcohol and alcohol ether. The flotation agent is selected from the above types, so that the firmness of sulfur adhering to bubbles is better improved, the stability of the bubbles is better, the flotation speed and selectivity of the sulfur are better, and more sulfur is promoted to adhere to the bubbles and float upwards. More preferably, the C6-C8 fatty alcohol is methyl isobutyl carbinol; preferably, the alcohol ether is selected from one or more of propylene glycol ether, propylene glycol monoalkyl ether.
Based on the flotation agent, the flotation effect is better in order to increase the adhesion amount of the sulfur on the bubbles. Preferably, the amount of the flotation agent is 5-50% of the weight of the arsenic sulfide-containing waste residue. More preferably, the amount of the flotation agent is 15-30% of the weight of the arsenic sulfide-containing waste residue.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
The arsenic sulfide-containing slag treated by the smelting wastewater vulcanization method and containing 8-10% of sulfuric acid comprises 53 wt% of arsenic sulfide and a small amount of metal sulfides such as copper sulfide, lead sulfide, iron sulfide and nickel sulfide.
Adding an oxidant into the arsenic sulfide-containing waste residue, wherein the oxidant is hydrogen peroxide, the dosage of the oxidant is 25% of the weight of the arsenic sulfide-containing waste residue, and carrying out an oxidation reaction at normal temperature and normal pressure so that arsenic sulfide in the arsenic sulfide-containing waste residue reacts to form sulfur and arsenic oxide, thereby obtaining reaction residues.
Mixing the reaction residue with a flotation agent, wherein the flotation agent is methyl isobutyl carbinol, the dosage of the methyl isobutyl carbinol is 5 percent of the weight of the arsenic sulfide-containing waste residue, and obtaining sulfur and residual slurry through flotation separation.
And adding a stabilizing agent into the residual slurry to stabilize arsenic ions in the slurry, wherein the stabilizing agent is hydroxyethylidene-1, 1-diphosphonic acid, tetrathiobisoxyformic acid and cement in a weight ratio of 4: 4:2, the dosage of the mixture is 20 percent of the weight of the arsenic sulfide-containing waste residue. The final stabilized product reaches the standard according to GB18598 and is buried.
And (3) sulfur product: the purity is 92.5 percent, and the yield of sulfur is 90 percent. And (3) treating the final stabilized product according to the national standard HJT299 on a solid waste leaching method to obtain arsenic-containing residue leachate, and testing that the concentration of arsenic in the arsenic-containing residue leachate is 1.15 mg/L.
Example 2
The arsenic sulfide-containing slag treated by the wastewater vulcanization method and containing 8-10% of sulfuric acid in the precious metal hydrometallurgy comprises 52 wt% of arsenic sulfide and a small amount of metal sulfides such as copper sulfide, lead sulfide, iron sulfide, nickel sulfide and the like.
Adding an oxidant into the arsenic sulfide-containing waste residue, wherein the oxidant is calcium chlorate, and the dosage of the oxidant is 60 percent of the weight of the arsenic sulfide-containing waste residue, so that the arsenic sulfide in the arsenic sulfide-containing waste residue is subjected to oxidation reaction to form sulfur and arsenic oxide, and further reaction residue is obtained.
Mixing the reaction residue with a flotation agent, wherein the flotation agent is methyl isobutyl carbinol, the dosage of the methyl isobutyl carbinol is 50% of the weight of the arsenic sulfide-containing waste residue, and obtaining sulfur and residual slurry through flotation separation.
And adding a stabilizing agent into the residual slurry to stabilize the arsenic ions in the slurry to reach the standard and fill the slurry, wherein the stabilizing agent is a mixture of 2-hydroxymethyl-4-mercaptothiophenol sodium salt, chitosan and cement in a weight ratio of 6:2:2, and the using amount of the stabilizing agent is 20% of the weight of the arsenic sulfide-containing waste residue. Finally, the stabilized product reaches the standard GB18598 and is buried.
And (3) sulfur product: the purity is 89%, the sulfur yield is 90%, the final stabilized product is treated according to the national standard HJT299 about a solid waste leaching method to obtain arsenic-containing residue leachate, and the concentration of arsenic in the arsenic-containing residue leachate is tested to be 1.05 mg/L.
Example 3
The only difference from example 1 is that the oxidizing agent is sodium hypochlorite, which is used in an amount of 45% by weight of the arsenic sulfide-containing waste residue.
And (3) sulfur product: the purity is 93 percent, the sulfur yield is 91 percent, the final stabilized product is treated according to the national standard HJT299 related to a solid waste leaching method to obtain arsenic-containing residue leachate, and the concentration of arsenic in the arsenic-containing residue leachate is tested to be 1.1 mg/L.
Example 4
The only difference from example 1 is that the oxidizing agent is a mixture of sodium chlorate and calcium chlorate in a weight ratio of 1:1, and the amount of the oxidizing agent is 35 percent of the weight of the arsenic sulfide-containing waste residue.
And (3) sulfur product: the purity is 93.2 percent, the sulfur yield is 91 percent, the final stabilized product is treated according to the national standard HJT299 about a solid waste leaching method to obtain arsenic-containing residue leachate, and the concentration of arsenic in the arsenic-containing residue leachate is tested to be 1.2 mg/L.
Example 5
The only difference from example 1 is that the oxidizing agent is a mixture of calcium hypochlorite and sodium hypochlorite in a weight ratio of 1.5:1, and the amount of the oxidizing agent is 30% of the weight of the arsenic sulfide-containing waste residue.
And (3) sulfur product: the purity is 93 percent, the sulfur yield is 90.5 percent, the final stabilized product is treated according to the national standard HJT299 related to a solid waste leaching method to obtain arsenic-containing residue leachate, and the concentration of arsenic in the arsenic-containing residue leachate is tested to be 1.15 mg/L.
Example 6
The only difference from example 1 is that the oxidant is a mixture of sodium chlorate, sodium hypochlorite and hydrogen peroxide in a weight ratio of 1:1: 1. The dosage of the waste residue is 25 percent of the weight of the waste residue containing arsenic sulfide.
And (3) sulfur product: the purity is 93.5 percent, the sulfur yield is 91 percent, the final stabilized product is treated according to the national standard HJT299 about a solid waste leaching method to obtain arsenic-containing residue leachate, and the concentration of arsenic in the arsenic-containing residue leachate is tested to be 1.15 mg/L.
Example 7
The only difference from example 1 is that the stabilizing agent is hydroxyethylidene-1, 1-diphosphonic acid, tetrathiobisethoxyformic acid and cement in a weight ratio of 6: 6:2, the dosage of the mixture is 60 percent of the weight of the arsenic sulfide-containing waste residue.
And (3) sulfur product: the purity is 92.5 percent, the sulfur yield is 90 percent, the final stabilized product is treated according to the national standard HJT299 related to a solid waste leaching method to obtain arsenic-containing residue leachate, and the concentration of arsenic in the arsenic-containing residue leachate is tested to be 1.3 mg/L.
Example 8
The only difference from example 1 is that the stabilizing agent is a mixture of 2-hydroxymethyl-4-mercaptothiophenol sodium salt, dextran and cement in a weight ratio of 8:4:2, the amount being 80% of the weight of the arsenic sulfide-containing waste residue.
And (3) sulfur product: the purity is 92 percent, the sulfur yield is 90 percent, the final stabilized product is treated according to the national standard HJT299 related to a solid waste leaching method to obtain arsenic-containing residue leachate, and the concentration of arsenic in the arsenic-containing residue leachate is tested to be 1.1 mg/L.
Example 9
The only difference from example 1 is that the flotation agent is propylene glycol ether.
And (3) sulfur product: the purity is 91 percent, the sulfur yield is 90 percent, the final stabilized product is treated according to the national standard HJT299 related to a solid waste leaching method to obtain arsenic-containing residue leachate, and the concentration of arsenic in the arsenic-containing residue leachate is tested to be 1.05 mg/L.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
as can be seen from the data of examples 1 to 9, the invention oxidizes arsenic sulfide into sulfur and arsenic oxide by a pretreatment method of adding an oxidant, then performs flotation separation to obtain sulfur, and finally stabilizes the arsenic oxide. Based on the process, the invention more effectively separates arsenic and sulfur, improves the utilization rate of sulfur, and promotes better resource utilization effect of arsenic sulfide-containing waste residues because more scenes of resource utilization of sulfur are available. Meanwhile, as the procedures of oxidation and flotation separation of sulfur are carried out in the earlier stage, the subsequent residual slurry can achieve a good stabilizing effect on arsenic ions by only adding a relatively small amount of stabilizing agent, the possibility of secondary pollution is avoided, the capacity increase ratio is smaller (the capacity increase ratio is the ratio of the initial waste residue to the agent to increase the volume), and the pressure for limiting the storage capacity of a landfill plant is smaller.
In particular, as can be seen from the data of examples 1 to 9, the oxidizing agent is selected from one or more of liquid oxidizing agents, chlorates, hypochlorites; preferably, the liquid oxidant is selected from hydrogen peroxide; preferably, the chlorate is selected from one or more of sodium chlorate, calcium chlorate, potassium chlorate and sodium perchlorate; preferably, the hypochlorite is selected from one or more of calcium hypochlorite, sodium hypochlorite, hypochlorous acid, potassium hypochlorite. When the oxidant is selected from the above types, the oxidation effect is better, more arsenic sulfide can be fully oxidized into sulfur, the recovery rate of the sulfur is higher, and meanwhile, the generated arsenic oxide and the sulfur are easier to separate in the subsequent flotation separation. Meanwhile, the oxidant of the type also has the advantages of mild reaction conditions, stable and easily controlled reaction system, no introduction of other impurities and the like. It should be noted that arsenic in arsenic sulfide slag exists in the form of trivalent arsenic ions, and it is inevitable that some of the trivalent arsenic ions are oxidized into pentavalent arsenic ions during the oxidation reaction. In order to reduce the possibility of oxidation of arsenic ions as much as possible, the oxidant is preferably hydrogen peroxide, or a mixture of sodium chlorate and calcium chlorate in a weight ratio of (1-2): 1, or a mixture of calcium hypochlorite and sodium hypochlorite in a weight ratio of (1-1.5): 1, or a mixture of sodium chlorate, sodium hypochlorite and hydrogen peroxide in a weight ratio of (1-1.5): 1. The hydrogen peroxide or the compound oxidant has better oxidation effect. In particular, in the oxidation process, sulfur ions can be oxidized into sulfur simple substances as much as possible, and trivalent arsenic ions can be reduced to be oxidized into arsenic ions with higher valence as much as possible. On one hand, the method is favorable for reducing the use amount of the oxidant, and on the other hand, the method is also favorable for promoting the subsequent stabilizing treatment of arsenic ions.
Particularly, as can be seen from the data of examples 1 to 2 and examples 7 to 8, the stabilizer is hydroxyethylidene-1, 1-diphosphonic acid and tetrathiobisformic acid, the curing agent is cement, and the weight ratio of the hydroxyethylidene-1, 1-diphosphonic acid to the tetrathiobisformic acid to the cement is (4-6): 2, or the stabilizer is 2-hydroxymethyl-4-mercaptothiophenol sodium salt and polysaccharide, including but not limited to chitosan, dextran and starch. The curing agent is cement, and the weight ratio of the 2-hydroxymethyl-4-mercapto thiophenol sodium salt to the polysaccharide to the cement is (6-8): 2-4): 2. By using the compound stabilizer and the curing agent, the arsenic ion curing effect is better while the addition amount of the stabilizer is reduced. The dosage of the stabilizing agent is 20 to 80 percent of the weight of the arsenic sulfide-containing waste residue. Within the range, the stabilized product has better stability, no secondary pollution, smaller compatibilization ratio, smaller pressure on reservoir capacity limitation of a landfill plant and better industrial application.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A treatment method of waste residue containing arsenic sulfide is characterized by comprising the following steps:
adding an oxidant into the arsenic sulfide-containing waste residue to enable arsenic sulfide in the arsenic sulfide-containing waste residue to be subjected to oxidation reaction to form sulfur and arsenic oxide, and further obtaining reaction residue;
mixing the reaction residue with a flotation agent, and performing flotation separation to obtain sulfur and residual slurry;
adding a stabilizing agent to the remaining slurry to stabilize arsenic ions therein.
2. The method for treating waste residue containing arsenic sulfide as claimed in claim 1, wherein the oxidant is selected from one or more of liquid oxidant, chlorate and hypochlorite;
preferably, the liquid oxidant is selected from hydrogen peroxide;
preferably, the chlorate is selected from one or more of sodium chlorate, calcium chlorate, potassium chlorate and sodium perchlorate;
preferably, the hypochlorite is selected from one or more of calcium hypochlorite, sodium hypochlorite, hypochlorous acid, potassium hypochlorite;
more preferably, the oxidant is the hydrogen peroxide, or a mixture of the sodium chlorate and the calcium chlorate in a weight ratio of (1-2): 1, or a mixture of the calcium hypochlorite and the sodium hypochlorite in a weight ratio of (1-1.5): 1, or a mixture of the sodium chlorate, the sodium hypochlorite and the hydrogen peroxide in a weight ratio of (1-1.5): 1.
3. The method for treating the waste residue containing the arsenic sulfide as claimed in claim 1, wherein the amount of the oxidant is 25-60% of the weight of the waste residue containing the arsenic sulfide.
4. The method for treating the waste residue containing the arsenic sulfide as claimed in claim 1, wherein the amount of the oxidant is 35-45% of the weight of the waste residue containing the arsenic sulfide.
5. The method for treating the arsenic sulfide-containing waste residue as claimed in any one of claims 1 to 4, wherein the stabilizing agent comprises a stabilizing agent, and the stabilizing agent is selected from one or more of aminocarboxylic acid chelating agent, organic polyphosphate chelating agent, sulfydryl-containing chelating agent and natural modified polymer trapping agent.
6. The method for treating arsenic sulfide-containing waste residue as claimed in claim 5, wherein the aminocarboxylic acid type chelating agent is one or more selected from the group consisting of ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetate, aminotriacetic acid salt, diethylenetriaminepentaacetate;
preferably, the organic polyphosphate chelating agent is selected from one or more of hydroxyethylidene-1, 1-diphosphonic acid, aminotrimethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, triethylene tetramine hexamethylene phosphonic acid, bis (1, 6-hexylene) triamine pentamethylene phosphonic acid, and polyaminopolyether tetramethylene phosphonic acid;
preferably, the thiol-containing chelating agent is selected from the group consisting of dithiocarboxylated acrylamide, 2-hydroxymethyl-4-mercaptothiophenol sodium salt, dithiocarbamate or tetrathiobisoxycarboxylic acid;
preferably, the natural modified polymer trapping agent is selected from one or more of starches, celluloses, plant gums and polysaccharides.
7. The method for treating the waste residue containing arsenic sulfide as claimed in any one of claims 1 to 6, wherein the stabilizing agent further comprises a curing agent, wherein the curing agent is selected from one or more of cement, fly ash and sodium silicate;
preferably, the weight ratio of the stabilizer to the curing agent is 1: 1-5;
more preferably, the stabilizer is the hydroxyethylidene-1, 1-diphosphonic acid and the tetrathiobisoxyformic acid, the curing agent is the cement, and the weight ratio of the hydroxyethylidene-1, 1-diphosphonic acid to the tetrathiobisoxyformic acid to the cement is (4-6): (4-6): 2; or the stabilizer is the 2-hydroxymethyl-4-mercaptothiophenol sodium salt and the polysaccharide, the curing agent is the cement, and the weight ratio of the 2-hydroxymethyl-4-mercaptothiophenol sodium salt to the polysaccharide to the cement is (6-8): 2-4): 2.
8. The method for treating the waste residue containing arsenic sulfide as claimed in any one of claims 1 to 5, wherein the amount of the stabilizing agent is 20-80% of the weight of the waste residue containing arsenic sulfide;
preferably, the dosage of the stabilizing agent is 40-60% of the weight of the arsenic sulfide-containing waste residue.
9. The method for treating the arsenic sulfide-containing waste residue as claimed in any one of claims 1 to 5, wherein the flotation agent is a mixture of one or more of pine oil, camphor oil, methyl phenolic acid, C6-C8 fatty alcohol and alcohol ether;
preferably, the C6-C8 fatty alcohol is methyl isobutyl carbinol;
preferably, the alcohol ether is selected from propylene glycol ether and/or propylene glycol monoalkyl ether.
10. The method for treating the waste residue containing the arsenic sulfide as claimed in claim 9, wherein the amount of the flotation agent is 5-50% of the weight of the waste residue containing the arsenic sulfide;
preferably, the amount of the flotation agent is 15-30% of the weight of the arsenic sulfide-containing waste residue.
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