CN114307031B - Arsenic slag solidification stabilization repair material and application method - Google Patents
Arsenic slag solidification stabilization repair material and application method Download PDFInfo
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- CN114307031B CN114307031B CN202111572926.4A CN202111572926A CN114307031B CN 114307031 B CN114307031 B CN 114307031B CN 202111572926 A CN202111572926 A CN 202111572926A CN 114307031 B CN114307031 B CN 114307031B
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to an arsenic slag solidification stabilization repair material and an application method thereof. The arsenic slag solidification and stabilization repair material comprises the following components: iron-manganese hydroxide, calcium complexing agent, oxidant and composite curing agent. The invention utilizes the specific stabilization effect of the iron-manganese hydroxide and the calcium complexing agent on arsenic, the oxidation effect of the oxidant on low-valent arsenic pollutants and the curing stabilization effect of the composite curing agent on stabilized products, the obtained curing stabilization repair material can perform curing stabilization on the arsenic pollutants in the arsenic slag through various mechanisms, the valence state of the arsenic can be completely converted into pentavalent arsenic, and the toxic leaching concentration of the arsenic is greatly reduced. The application method has the advantages of simple process, environmental protection, high efficiency, economy and the like.
Description
Technical Field
The invention belongs to the field of hazardous waste disposal, and particularly relates to an arsenic slag solidification stabilization repair material and application thereof.
Background
The arsenic slag is arsenic-containing solid waste which is produced in the non-ferrous metal smelting process, does not have economic recovery value and belongs to dangerous waste, is mainly derived from the non-ferrous metal smelting process, belongs to heavy pollution waste, and can be divided into oxide arsenic slag, arsenate arsenic slag, sulfide arsenic slag and mixtures thereof according to the main existing form of arsenic. Unlike general arsenic contaminated soils, common arsenic slag species have very high arsenic content and specific compositions such as sulfide and calcium based components, and their physicochemical properties are difficult to control. Therefore, properly treating the arsenic sulfide slag has important significance in the aspects of industrial production, safety, environmental protection and the like. As hazardous waste, the arsenic leaching concentration in the arsenic slag needs to be treated to reach the entrance standard by a certain treatment means before entering the field.
At present, two main treatment modes of arsenic slag are provided, one is solidification and stabilization treatment, the other is resource treatment, and the solidification and stabilization treatment is the most extensive method for treating the arsenic slag. CN106823238A discloses a hydrothermally stable curing treatment method for arsenic sulfide slag, which comprises the steps of adjusting the liquid-solid ratio, pH and Eh of the arsenic sulfide slag, then feeding the arsenic sulfide slag into a high-temperature high-pressure hydrothermal reaction kettle for curing reaction, and controlling reaction conditions and process parameters to realize hydrothermally stable curing of the arsenic sulfide slag. CN105963902A discloses a method for harmless treatment of arsenic sulfide slag, which comprises the steps of mixing arsenic sulfide slag with water at room temperature, adding sodium sulfide for reaction to obtain a mixture, adding an oxidant for oxidation reaction, then adding iron salt or aluminum salt for reaction, and then adding cement. CN104230242A discloses a method for preparing harmless cured brick from high-arsenic sludge, which comprises adding 20-60 parts of high-arsenic sludge, 0-20 parts of industrial waste residue, 1-3 parts of organic sulfur and organic amine arsenic chelating agent, 40-79 parts of curing material (cement, special cementing material and curing excitant) and 10-20 parts of water according to parts by mass, and pressing under 10-50 MPa. CN104525555A discloses a stabilization treatment method and equipment for arsenic slag, which is to add ferrous salt and sieved arsenic slag into a hopper according to the molar ratio of Fe to As of 1.8-3.0, stir for 3-7min, and then add concentrated sulfuric acid and stir for 3-7min.
The method can reduce the arsenic leaching concentration of the arsenic slag, but the arsenic slag solidification or stabilization repair technology has certain defects, wherein a single material or a rough process is mostly utilized, a large amount of materials are consumed, the energy consumption is high, the cost is high, the arsenic leaching concentration is difficult to reach the standard, and the large-scale treatment is difficult to realize.
Therefore, how to provide a simple, environment-friendly, efficient and economical treatment method for treating arsenic slag substances is still a technical problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the problems in the prior art, the invention provides an arsenic slag solidification and stabilization repair material and an application method thereof, the arsenic slag solidification and stabilization repair material is a composite multicomponent stepwise-used arsenic slag repair material, and the repair material can not only reduce the arsenic leaching concentration in common arsenic slag, but also avoid the secondary dissolution, migration and leakage of arsenic substances in the arsenic slag. The application method has the advantages of simple process, environmental protection, high efficiency, economy and the like.
In order to achieve the technical effect, the invention adopts the following technical scheme:
the invention provides an arsenic slag solidification stabilization repair material, which comprises the following components: iron-manganese hydroxide, calcium complexing agent, oxidant and composite curing agent.
According to the arsenic slag solidification and stabilization repair material, the characteristic utilization rate of the self element composition is maximized, the synergistic effect of the four components can be further utilized, the solidification, stabilization, oxidation and other effects can be simultaneously realized, and the arsenic slag product with low leaching and toxicity stabilization is quickly formed, so that the mobility is further reduced, and the phenomena of toxicity rebound and the like are avoided.
As a preferable technical scheme, the arsenic slag solidification and stabilization repair material comprises the following components in parts by weight: 1.2-13 parts of iron-manganese hydroxide, 0.9-8.5 parts of calcium complexing agent, 0.9-8.5 parts of oxidant and 5-20 parts of composite curing agent.
The amount of the iron-manganese hydroxide is 1.2 to 13 parts by weight, for example, 1.2 parts, 3 parts, 5 parts, 7 parts, 9 parts, 11 parts or 13 parts by weight, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The calcium complex agent is present in an amount of 0.9 to 8.5 parts by weight, for example 0.9, 2, 4, 6, 8 or 8.5 parts by weight, but not limited to the recited amounts, and other values not recited in the numerical ranges are also applicable.
The oxidizing agent is present in an amount of 0.9 to 8.5 parts by weight, for example 0.9, 2, 4, 6, 8 or 8.5 parts by weight, but is not limited to the recited amounts, and other values not recited within the numerical ranges are equally applicable.
The weight part of the composite curing agent is 5-20 parts, such as 5 parts, 7 parts, 9 parts, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts or 20 parts, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
In the invention, the mass ratio of the iron-manganese hydroxide, the calcium complexing agent, the oxidant and the composite curing agent is (5-10) to (3-6) to (10-15), and can be, for example, 5.
In the invention, the contents of the four components are interacted, and the curing and stabilizing effect of the system is poor due to too little content of any component, so that the effect of reducing the leaching concentration of arsenic is poor and the pH imbalance can be caused; in the invention, the content of the iron-manganese hydroxide is too low, and the stabilizing effect on arsenic is poor; the content of the calcium complexing agent is too low, so that the stabilizing effect of the iron-manganese hydroxide cannot be exerted; in the invention, if the content of the oxidant is too low, the arsenic slag with relatively high content of trivalent arsenic cannot be stabilized; in the invention, if the content of the composite curing agent is too low, the arsenic leaching concentration cannot meet the standard requirement of hazardous waste landfill.
As a preferred technical solution of the present invention, the preparation method of the iron-manganese hydroxide comprises: and mixing soluble ferric salt with a solvent, adjusting the pH value, carrying out first heat treatment, cooling, mixing with soluble manganese salt, and carrying out second heat treatment to obtain the ferro-manganese hydroxide.
Preferably, the temperature of the first heat treatment is 80-120 ℃, for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, etc., but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the time of the first heat treatment is 1 to 3 hours, for example, 1 hour, 1.4 hours, 1.8 hours, 2.2 hours, 2.6 hours or 3 hours, etc., but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the temperature of the second heat treatment is 80 to 120 ℃, for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃ and the like, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the time of the second heat treatment is 0.5 to 1.5 hours, for example, 0.5 hour, 0.7 hour, 0.9 hour, 1.1 hour, 1.3 hour or 1.5 hour, etc., but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
According to the invention, the ferro-manganese hydroxide is prepared through two-step heat treatment, the ferro-manganese hydroxide is modified by manganese, and has a flower cluster-shaped nanosheet structure, high surface active site density and strong activity, and manganese element is enriched on the surface of the nanosheet.
As a preferred embodiment of the present invention, the soluble iron salt includes any one or a combination of at least two of ferrous sulfate, ferrous chloride, ferric sulfate, ferric chloride or ferric nitrate, and the combination is typically but not limited to: a combination of ferrous sulfate and ferrous chloride, a combination of ferric sulfate and ferric chloride, a combination of ferric chloride and ferric nitrate, or the like, preferably ferric chloride.
Preferably, the solvent comprises ethanol and/or water.
Preferably, the pH is adjusted to a pH of 8-10, which may be, for example, 8, 8.5, 9, 9.5, or 10.0, etc.
Preferably, the soluble manganese salt comprises manganese chloride and/or nitrate, preferably manganese chloride.
Preferably, the soluble manganese salt has a manganese impregnation amount of 3-5%, such as 3%, 3.5%, 4%, 4.5%, or 5%.
As a preferable technical scheme of the invention, the calcium complexing agent is a mixture of calcium oxide and hydrated lime.
Preferably, the mass ratio of the calcium oxide to the hydrated lime is (1-3) to 1; for example, 1.
Preferably, the preparation method of the calcium complexing agent comprises the following steps: and carrying out heat treatment on the calcium oxide and the hydrated lime at the temperature of 80-100 ℃ for 5-7h to obtain the calcium complexing agent.
According to the invention, the stabilization effect of the manganese modified iron hydroxide and the calcium complexing agent is utilized, so that the arsenic pollutants in the common arsenic slag can be efficiently and chemically stabilized, and most of the arsenic pollutants are converted into low-toxicity and low-mobility arsenic stabilization products. The manganese modified iron hydroxide can generate synergistic effect with the calcium complexing agent, the reaction product produced in the stabilizing process has small particles and high activity, can quickly capture a large amount of arsenic pollutants, has high reaction capacity, and can realize the stabilization of the large amount of arsenic pollutants.
In the invention, the component A is obtained by mixing the iron-manganese hydroxide as the component A1 and the calcium complexing agent as the component A2; wherein, the component A1 is a main stabilizing component, and the component A2 is an auxiliary stabilizing component.
In a preferred embodiment of the present invention, the oxidizing agent comprises a sodium hypochlorite solution and/or a potassium permanganate solution.
Preferably, the sodium hypochlorite solution has a solids content of 10-12%, for example, 10%, 10.2%, 10.4%, 10.6%, 10.8%, 11%, 11.2%, 11.4%, 11.6%, 11.8%, 12%, or the like.
Preferably, the pH of the sodium hypochlorite solution is adjusted to 10.8-11.2, which may be, for example, 10.8, 10.9, 11.0, 11.1, or 11.2, etc.
Preferably, the pH of the potassium permanganate solution is adjusted to 9-11, which may be, for example, 9, 9.5, 10, 10.5, or 11, and the like.
In the invention, the oxidant can rapidly oxidize low-valence arsenic in common arsenic slag, so that the mobility and leaching toxicity of the low-valence arsenic slag are greatly reduced, and the stable components are easily stabilized.
In a preferred embodiment of the present invention, the composite curing agent is a mixture of PAM (polyacrylamide), silicate and cement.
Preferably, the mass ratio of the PAM, the silicate and the cement is 1.
Preferably, the PAM is a particulate APAM (anionic polyacrylamide).
Preferably, the silicate comprises Na 2 SiO 3 、Na 2 SiO 3 ·5H 2 O or Na 4 SiO 4 Of the group of (a), typical but non-limiting examples of which are: na (Na) 2 SiO 3 And Na 2 SiO 3 ·5H 2 Combination of O or Na 2 SiO 3 ·5H 2 O and Na 4 SiO 4 Combinations of (A), (B) and (C), preferably Na 2 SiO 3 。
Preferably, the cement comprises any one or a combination of at least two of types 42.5, 42.5R, 52.5 or 52.5R, typical but non-limiting examples of which are: a combination of 42.5 type and 42.5R type, a combination of 52.5 type and 52.5R type, etc., preferably 42.5R type.
The composite curing agent has the advantages of organic curing agents, inorganic curing agents and curing materials sold in the market, has wide applicability, and can meet the curing requirements of most types of arsenic slag.
The invention also provides an application method of the arsenic slag solidification and stabilization repair material, which comprises the following steps:
(1) Uniformly mixing arsenic slag powder, iron-manganese hydroxide, calcium complexing agent, oxidant and water, and then carrying out first maintenance treatment to obtain first-stage maintenance arsenic slag;
(2) And (3) uniformly mixing the composite curing agent, the first-stage curing arsenic slag obtained in the step (1) and water, and then carrying out second curing treatment to obtain second-stage curing arsenic slag.
As a preferable technical scheme of the invention, the mass ratio of the total mass of the iron-manganese hydroxide, the calcium complexing agent and the oxidant in the step (1) to the arsenic slag powder is (0.03-0.3): 1, and can be, for example, 0.03.
Preferably, the time of the first curing treatment in step (1) is 1 to 3 days, and may be, for example, 1, 1.5, 2, 2.5, 3, or the like.
Preferably, the water content of the arsenic slag cured in the first stage in the step (1) is 10-20%, for example, 10%, 12%, 14%, 16%, 18%, 20%, etc.
As a preferred technical solution of the present invention, the mass ratio of the composite curing agent to the arsenic slag powder in the step (2) is (0.05-0.2): 1, and may be, for example, 0.05.
Preferably, the time of the second curing treatment in the step (2) is 10-20 days, such as 10, 12, 14, 16, 18 or 20.
Preferably, the water content of the arsenic slag cured in the second stage of step (2) is 40-60%, for example, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, or 60%.
Compared with the prior art, the invention has the following beneficial effects:
(1) The iron-manganese hydroxide and calcium complexing agent can play a common stabilizing role, the reaction product of the iron-manganese hydroxide and the calcium complexing agent has high reaction activity and high reaction quantity on arsenic pollutants, the oxidizing effect of an oxidizing agent on low-valent arsenic pollutants and the curing stabilizing effect of a composite curing agent on the stabilizing product can be suitable for curing and stabilizing repair of arsenic slag of different types, and the iron-manganese hydroxide and calcium complexing agent has good repairing effect, is stable for a long time, has no secondary pollution and has high comprehensive cost performance;
(2) The arsenic slag solidification and stabilization repair material can convert arsenic pollutants in arsenic slag into low-toxicity and low-mobility arsenic stabilization products, and the leaching concentration of arsenic is reduced to be below 0.5 mg/L;
(3) The application method has the advantages of simple process, environmental protection, high efficiency, economy and the like.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the following examples are set forth herein. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an arsenic slag solidification and stabilization repair material and an application method thereof, wherein the arsenic slag solidification and stabilization repair material comprises 0.7g of iron-manganese hydroxide, 0.4g of calcium complexing agent, 0.4g of oxidant and 1.2g of composite curing agent.
The preparation method of the ferro-manganese hydroxide comprises the following steps: dissolving 1.622g of ferric chloride in a mixed solution of 100mL of ethanol and 100mL of water, adjusting the pH value of the mixed solution to 9, transferring the mixed solution to a polytetrafluoroethylene reaction kettle, carrying out heat treatment at 100 ℃ for 2h, adding 0.0503g of manganese chloride after cooling, carrying out heat treatment at 100 ℃ for 1h, cooling, separating, drying and grinding until the particle size is less than 0.1mm, wherein the impregnation amount of manganese is 4%.
The calcium complexing agent is a mixture of calcium oxide and hydrated lime, and the preparation method comprises the following steps: 2g of calcium oxide and 1g of hydrated lime are subjected to heat treatment at 90 ℃ for 6h, and are dried and ground until the particle size is less than 0.1mm, wherein the mass ratio of the calcium oxide to the hydrated lime is 2.
The oxidant is sodium hypochlorite solution with solid content of 11%, and the pH value of the sodium hypochlorite solution is adjusted to 11.
The composite curing agent is APAM and Na 2 SiO 3 And 42.5R type cement, the APAM, na 2 SiO 3 And 42.5 the mass ratio of the R-type cement is 1.
The application method comprises the following steps:
(1) Grinding original arsenic slag into arsenic slag powder with the particle size of less than 2mm, adding a ferro-manganese hydroxide, a calcium complexing agent and an oxidant, uniformly mixing, adding water to adjust the water content to 15%, uniformly mixing, and performing first maintenance treatment for 2 days to obtain first-stage maintenance arsenic slag, wherein the mass ratio of the total mass of the ferro-manganese hydroxide, the calcium complexing agent and the oxidant to the arsenic slag powder is 0.15;
(2) And (2) uniformly mixing a composite curing agent with the arsenic slag cured in the first stage in the step (1), adding water to adjust the water content to 50%, uniformly mixing, and performing second curing treatment for 15 days to obtain arsenic slag cured in the second stage, wherein the mass ratio of the composite curing agent to the arsenic slag powder is 0.1.
Example 2
The embodiment provides an arsenic slag solidification and stabilization repair material and an application method thereof, and the arsenic slag solidification and stabilization repair material comprises 1.3g of iron-manganese hydroxide, 0.09g of calcium complexing agent, 0.09g of oxidant and 0.5g of composite curing agent.
The preparation method of the ferro-manganese hydroxide comprises the following steps: dissolving 1.622g of ferric chloride in a mixed solution of 100mL of ethanol and 100mL of water, adjusting the pH value of the mixed solution to 8, transferring the mixed solution to a polytetrafluoroethylene reaction kettle, carrying out heat treatment at 80 ℃ for 3h, adding 0.0377g of manganese chloride after cooling, carrying out heat treatment at 80 ℃ for 1.5h, cooling, separating, drying and grinding until the particle size is less than 0.1mm.
The calcium complexing agent is a mixture of calcium oxide and hydrated lime, and the preparation method comprises the following steps: 1g of calcium oxide and 1g of hydrated lime are subjected to heat treatment at 80 ℃ for 7h, and are dried and ground until the particle size is less than 0.1mm, wherein the mass ratio of the calcium oxide to the hydrated lime is 1.
The oxidant is sodium hypochlorite solution with solid content of 10%, and the pH value of the sodium hypochlorite solution is adjusted to 10.8.
The composite curing agent is APAM and Na 2 SiO 3 And 42.5R type cement, the APAM, na 2 SiO 3 And 42.5 mass ratio of the R-type cement is 1.
The application method comprises the following steps:
(1) Grinding the original arsenic slag into arsenic slag powder with the particle size of less than 2mm, then adding a ferro-manganese hydroxide, a calcium complexing agent and an oxidant, uniformly mixing, adding water to adjust the water content to 10%, uniformly mixing, and then carrying out first maintenance treatment for 1 day to obtain first-stage maintenance arsenic slag, wherein the mass ratio of the total mass of the ferro-manganese hydroxide, the calcium complexing agent and the oxidant to the mass of the arsenic slag powder is 0.03;
(2) And (2) uniformly mixing a composite curing agent with the arsenic slag obtained in the first-stage curing in the step (1), adding water to adjust the water content to 40%, uniformly mixing, and performing second curing treatment for 10 days to obtain second-stage cured arsenic slag, wherein the mass ratio of the composite curing agent to the arsenic slag powder is 0.05.
Example 3
The embodiment provides an arsenic slag solidification and stabilization repair material and an application method thereof, and the arsenic slag solidification and stabilization repair material comprises 0.12g of iron-manganese hydroxide, 0.85g of calcium complexing agent, 0.85g of oxidant and 2.0g of composite curing agent.
The preparation method of the iron-manganese hydroxide comprises the following steps: dissolving 1.622g of ferric chloride in a mixed solution of 100mL of ethanol and 100mL of water, adjusting the pH value of the mixed solution to 10, transferring the mixed solution to a polytetrafluoroethylene reaction kettle, carrying out heat treatment at 120 ℃ for 1h, adding 0.0629g of manganese chloride after cooling, carrying out heat treatment at 120 ℃ for 0.5h, cooling, separating, drying and grinding until the particle size is less than 0.1mm, wherein the impregnation amount of manganese is 5%.
The calcium complexing agent is a mixture of calcium oxide and hydrated lime, and the preparation method comprises the following steps: 3g of calcium oxide and 1g of hydrated lime are subjected to heat treatment at 100 ℃ for 5h, and are dried and ground until the particle size is less than 0.1mm, wherein the mass ratio of the calcium oxide to the hydrated lime is 3.
The oxidant is a sodium hypochlorite solution with a solid content of 12%, and the pH of the sodium hypochlorite solution is adjusted to 11.2.
The composite curing agent is APAM and Na 2 SiO 3 And 42.5R type cement, the APAM, na 2 SiO 3 And the mass ratio of the 42.5R type cement is 1.
The application method comprises the following steps:
(1) Grinding original arsenic slag into arsenic slag powder with the particle size of less than 2mm, adding a ferro-manganese hydroxide, a calcium complexing agent and an oxidant, uniformly mixing, adding water to adjust the water content to 20%, uniformly mixing, and performing first maintenance treatment for 3 days to obtain first-stage maintenance arsenic slag, wherein the mass ratio of the total mass of the ferro-manganese hydroxide, the calcium complexing agent and the oxidant to the arsenic slag powder is 0.3;
(2) And (2) uniformly mixing a composite curing agent and the arsenic slag maintained in the first stage in the step (1), adding water to adjust the water content to 60%, uniformly mixing, and performing second maintenance treatment for 20 days to obtain second-stage maintained arsenic slag, wherein the mass ratio of the composite curing agent to the arsenic slag powder is 0.2.
Example 4
This example differs from example 1 only in that ferric chloride was replaced by ferrous sulphate and the oxidant was potassium permanganate solution, the pH was adjusted to 10 and the other conditions were the same as in example 1.
Example 5
This example differs from example 1 only in that the manganese chloride was replaced by manganese nitrate and the oxidizing agent was potassium permanganate solution, the pH was adjusted to 10, and the other conditions were the same as in example 1.
Example 6
The difference between the present example and example 1 is only that the mass ratio of the total mass of the iron-manganese hydroxide, the calcium complexing agent and the oxidant to the arsenic slag powder in step (1) is 0.4.
Example 7
The present example is different from example 1 only in that the water content was adjusted to 7% in the step (1) and 30% in the step (2), and the other conditions were the same as example 1.
Example 8
This example is different from example 1 only in that the water content was adjusted to 25% in the step (1) and to 65% in the step (2), and the other conditions were the same as example 1.
Example 9
This example is different from example 1 only in that the weight of the iron manganese hydroxide is 0.1g, and the other conditions are the same as example 1.
Example 10
This example is different from example 1 only in that the calcium complexing agent has a mass of 0.05g, and the other conditions are the same as example 1.
Example 11
This example differs from example 1 only in that the mass of the oxidizing agent was 0.05g, and the other conditions were the same as example 1.
Example 12
The present example is different from example 1 only in that the mass of the composite curing agent is 0.5g, and the other conditions are the same as example 1.
Comparative example 1
The comparative example provides an arsenic slag solidification and stabilization repair material and an application method thereof, and the arsenic slag solidification and stabilization repair material comprises 0.7g of ferric hydroxide, 0.4g of calcium complexing agent, 0.4g of oxidant and 1.2g of composite curing agent.
The preparation method of the ferric hydroxide comprises the following steps: dissolving 1.622g of ferric chloride in a mixed solution of 100mL of ethanol and 100mL of water, adjusting the pH value of the mixed solution to 10, transferring the mixed solution to a polytetrafluoroethylene reaction kettle, carrying out heat treatment at 120 ℃ for 1h, cooling, separating, drying and grinding until the particle size is less than 0.1mm; the rest was the same as in example 1.
Comparative example 2
The comparative example is different from example 1 only in that the arsenic slag solidification stabilization repair material does not contain iron manganese hydroxide, and other conditions are the same as example 1.
Comparative example 3
The comparative example is different from the example 1 only in that the arsenic slag solidification and stabilization repair material does not contain a calcium complexing agent, and other conditions are the same as the example 1.
Comparative example 4
The comparative example is different from the example 1 only in that the arsenic slag solidification stabilization repair material does not contain an oxidizing agent, and other conditions are the same as the example 1.
Comparative example 5
The comparative example is different from the example 1 only in that the arsenic slag solidification and stabilization repair material does not contain a composite curing agent, and other conditions are the same as the example 1.
The performance test methods and results of the above examples and comparative examples are as follows:
and (3) performance testing: the test was carried out according to the "solid waste leaching toxicity leaching method horizontal shaking method" (HJ 557-2010).
TABLE 1
From table 1, the following points can be derived: the arsenic slag solidification and stabilization repair material prepared in the embodiment 1-5 has a good repair effect on arsenic slag; when the method is applied to the embodiment 6, the mass ratio of the four components to the arsenic slag is too high, a large amount of water in leaching liquor needs to be consumed in the reaction process, and the actual solid-liquid ratio is greatly increased, so that the arsenic leaching concentration is increased; the repair material prepared in the embodiment 7 has the disadvantages of too little water addition, too low water content, insufficient mass transfer and contact reaction of the repair material and poor repair effect in application; in the repairing material prepared in the embodiment 8, when the repairing material is applied, too much water is added, the water content is too high, the repairing material reacts too fast, part of components do not contact with pollutants sufficiently in time, namely, react with each other, and the effect of the repairing material is not fully reflected; in example 9, the addition amount of the iron-manganese hydroxide is too low, and the stabilization effect on the arsenic slag is poor; in the embodiment 10, the addition amount of the calcium complexing agent is too low, so that the stabilizing effect on the iron-manganese hydroxide cannot be exerted, and the repairing effect on the arsenic slag is poor; in example 11, the addition amount of the oxidant is too low, and the arsenic slag with high content cannot be stabilized; in example 12, the amount of the composite curing agent added was too low, and the effect of stabilizing and repairing the arsenic slag was poor.
The comparative example 1 contains ferric hydroxide, and the ferric hydroxide is not modified by manganese, so that the prepared repairing material has poor stabilizing and repairing effects on arsenic slag; the fact that the comparative example 2 does not contain iron-manganese hydroxide, the comparative example 3 does not contain calcium complexing agent, the comparative example 4 does not contain oxidant and the comparative example 5 does not contain composite curing agent has a reduced curing and stabilizing effect on the arsenic slag, so that the arsenic leaching concentration is increased, shows that a synergistic effect exists among the four repairing components, and the curing and stabilizing effect on the arsenic slag is reduced due to the lack of any one repairing component.
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 (24)
1. The arsenic slag solidification and stabilization repair material is characterized by comprising the following components in parts by weight: 1.2-13 parts of iron-manganese hydroxide, 0.9-8.5 parts of calcium complexing agent, 0.9-8.5 parts of oxidant and 5-20 parts of composite curing agent;
the preparation method of the iron-manganese hydroxide comprises the following steps: mixing soluble ferric salt and a solvent, adjusting the pH value, carrying out first heat treatment, cooling, mixing with soluble manganese salt, and carrying out second heat treatment to obtain the ferro-manganese hydroxide; the pH is adjusted to 8-10; the temperature of the first heat treatment is 80-120 ℃; the temperature of the second heat treatment is 80-120 ℃;
the calcium complexing agent is a mixture of calcium oxide and hydrated lime; the preparation method of the calcium complexing agent comprises the following steps: carrying out heat treatment on calcium oxide and hydrated lime at 80-100 ℃ for 5-7h to obtain the calcium complexing agent;
the oxidant comprises a sodium hypochlorite solution and/or a potassium permanganate solution; adjusting the pH value of the sodium hypochlorite solution to 10.8-11.2; the pH value of the potassium permanganate solution is adjusted to 9-11;
the composite curing agent is a mixture of PAM, silicate and cement.
2. The arsenic slag solidification, stabilization and repair material as claimed in claim 1, wherein the first heat treatment is performed for 1 to 3 hours.
3. The arsenic slag solidification stabilization repair material of claim 1, wherein the second heat treatment is performed for 0.5 to 1.5 hours.
4. The arsenic slag solidification stabilization repair material of claim 1, wherein the soluble iron salt comprises any one or a combination of at least two of ferrous sulfate, ferrous chloride, ferric sulfate, ferric chloride, or ferric nitrate.
5. The arsenic slag solidification, stabilization and remediation material of claim 4, wherein the soluble iron salt is ferric chloride.
6. The arsenic slag solidification-stabilization restorative material of claim 1, wherein the solvent comprises ethanol and/or water.
7. The arsenic slag solidification-stabilizing remediation material of claim 1, wherein the soluble manganese salt comprises manganese chloride and/or manganese nitrate.
8. The arsenic slag solidification stabilization repair material of claim 7, wherein the soluble manganese salt is manganese chloride.
9. The arsenic slag solidification stabilization repair material of claim 1, wherein the soluble manganese salt has an impregnation amount of manganese element of 3 to 5%.
10. The arsenic slag solidification stabilization repair material of claim 1, wherein the mass ratio of the calcium oxide to the hydrated lime is (1-3): 1.
11. The arsenic slag solidification stabilization repair material of claim 1, wherein the sodium hypochlorite solution has a solid content of 10-12%.
12. The arsenic slag solidification and stabilization repair material as claimed in claim 1, wherein the mass ratio of the PAM to the silicate to the cement is 1.
13. The arsenic slag solidification stabilization repair material of claim 1 wherein the PAM is a granular APAM.
14. The arsenic slag solidification-stabilized repair material of claim 1, wherein the silicate comprises Na 2 SiO 3 、Na 2 SiO 3 ·5H 2 O or Na 4 SiO 4 Or a combination of at least two thereof.
15. The arsenic slag solidification-stabilization restorative material of claim 14, wherein the silicate is Na 2 SiO 3 。
16. The arsenic slag solidification stabilization restorative material of claim 1, wherein the cement comprises any one of or a combination of at least two of 42.5, 42.5R, 52.5, or 52.5R types.
17. The arsenic slag solidification stabilization repair material of claim 16, wherein the cement is 42.5R-type.
18. The application method of the arsenic slag solidification and stabilization repair material as claimed in any one of claims 1 to 17, is characterized by comprising the following steps:
(1) Uniformly mixing arsenic slag powder, iron-manganese hydroxide, calcium complexing agent, oxidant and water, and then carrying out first maintenance treatment to obtain first-stage maintenance arsenic slag;
(2) And (2) uniformly mixing the composite curing agent, the first-stage cured arsenic slag obtained in the step (1) and water, and then carrying out second curing treatment to obtain second-stage cured arsenic slag.
19. The application method of claim 18, wherein the mass ratio of the total mass of the iron-manganese hydroxide, the calcium complexing agent and the oxidant in the step (1) to the arsenic slag powder is (0.03-0.3): 1.
20. The use of the method as claimed in claim 18, wherein the first curing treatment of step (1) is carried out for a period of 1 to 3 days.
21. The application method of claim 18, wherein the water content of the arsenic slag maintained in the first stage in the step (1) is 10-20%.
22. The application method of claim 18, wherein the mass ratio of the composite curing agent to the arsenic slag powder in the step (2) is (0.05-0.2): 1.
23. The use of the method as claimed in claim 18, wherein the time of the second curing treatment in step (2) is 10 to 20 days.
24. The application method of claim 18, wherein the water content of the arsenic slag cured in the second stage in the step (2) is 40-60%.
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