CN116002935A - Comprehensive treatment method for ferrite-containing water - Google Patents
Comprehensive treatment method for ferrite-containing water Download PDFInfo
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Abstract
The invention provides a method for comprehensively treating ferrite-containing water, and relates to the field of water treatment. According to the method, iron-removing pretreatment, copper-collecting by vulcanization and neutralization treatment are sequentially carried out on ferrous water, iron-removing turbid liquid is directly input into a copper-collecting section by vulcanization without flocculation during the iron-removing pretreatment, and meanwhile, an oxidant is used for treatment during the neutralization process, so that neutralization overflow and filter-pressing liquid obtained during the neutralization process can meet the discharge standard, and deep purification of ferrous water is realized; the process does not produce de-ironing slag, greatly reduces the production of solid waste, effectively reduces valuable substance copper lost with the liquid phase of the iron slag, and improves the copper recovery rate of the whole acid water treatment system. Through the mode, the invention can realize the effective treatment of the ferrite-containing water by a simple process and a low-cost medicament, the treated water body and the neutralization slag meet the corresponding emission requirements, and the invention does not produce dangerous wastes such as iron slag and the like, thereby having obvious economic benefit, environmental benefit and social benefit.
Description
Technical Field
The invention relates to the technical field of environmental protection and water treatment, in particular to a method for comprehensively treating ferrite-containing water.
Background
The sulfur-rich mineral deposit of nonferrous metal mine contains a great amount of sulfide minerals, and under the action of air, water and microorganism, a series of physical and chemical reactions such as weathering, leaching, oxidation and hydrolysis are carried out to gradually form acidic liquid containing sulfuric acid, so that serious pollution is caused to the surrounding environment of the mining area. Therefore, it is necessary to treat the acidic water to protect the surrounding environment of the mining area.
Because the acidic water is generally rich in valuable substances such as copper, iron and the like, the treatment method commonly adopted at present is a fractional precipitation method, namely, iron removal pretreatment is carried out firstly, valuable substances copper is recovered through a vulcanization method, and then other heavy metals in the acidic water are removed through a lime neutralization method (HDS method). For example, patent publication No. CN108101253A provides a method for treating heavy metal wastewater, which comprises the steps of firstly carrying out iron removal operation, adjusting the pH value of the wastewater to 4-5, adding a flocculating agent, and settling to remove iron ions in the wastewater; then adding sodium sulfide and flocculant into supernatant fluid obtained in the iron removal operation, settling to remove copper ions in the wastewater, and carrying out copper precipitation operation; and then regulating the pH value of the supernatant obtained in copper precipitation operation to 6-7, adding a flocculating agent, and settling to remove heavy metal ions in the wastewater to obtain clear water which is discharged up to the standard.
However, although the method treats the wastewater containing heavy metals into clear water which can be discharged after reaching standards, when the content of copper, arsenic, beryllium and other metals in the wastewater is relatively high, the indexes of leaching toxicity (copper exceeding standard) and toxic substance content (arsenic exceeding standard) of iron-removing slag formed after adding flocculating agent in the iron-removing operation process can not meet the requirements of general industrial solid waste, and the method belongs to dangerous waste. Thus, not only the construction investment and the running cost of the whole water treatment project are seriously increased, but also the hidden danger of the environment is increased. In addition, the method can generate neutralization slag after adding flocculant in the neutralization operation process for sedimentation, and if the iron-removing operation is omitted to avoid the generation of the iron-removing slag, the neutralization slag generated in the subsequent neutralization operation cannot meet the requirements of general industrial solid wastes. Therefore, how to reasonably optimize the treatment process of the iron-containing acidic water, furthest reduce the generation of iron-removing slag, and meanwhile, the neutralization slag generated in the water treatment process can meet the requirements of general industrial solid wastes, thereby being a research hot spot for the treatment of the iron-containing acidic water at present.
In view of the foregoing, there is a need for an improved method for the integrated remediation of ferrous water to address the above-mentioned problems.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for comprehensively treating ferrite-containing water, which is characterized in that the water treatment process is reasonably designed, reaction parameters such as pH, ORP value and the like are effectively controlled, the generation of dangerous waste iron-removing slag is avoided, the generated neutralization slag meets the requirements of general industrial solid waste, and meanwhile, the efficient recovery of valuable substance copper is realized.
In order to achieve the above purpose, the invention provides a method for comprehensively treating ferrite-containing water, which comprises the following steps:
s1, inputting ferrite-containing water into an iron removal reaction tank, and adjusting the pH value to obtain an iron removal turbid liquid;
s2, inputting the deironing turbid liquid obtained in the step S1 into a vulcanization reaction tank, and adding a vulcanizing agent to adjust the ORP value to obtain a copper-collecting turbid liquid for vulcanization; adding a flocculating agent into the copper-collecting turbid liquid, and carrying out solid-liquid separation by a vulcanizing thickener to obtain vulcanizing underflow and vulcanizing overflow; refluxing one part of the sulfidizing underflow into the sulfidizing reaction tank, and performing filter pressing dehydration treatment on the other part of the sulfidizing underflow to obtain first filter pressing residues and first filter pressing liquid;
s3, inputting the vulcanization overflow obtained in the step S2 and the first filter pressing liquid into a neutralization reaction tank as neutralization liquid, adjusting the pH value, and simultaneously introducing an oxidant to fully react to obtain neutralization turbid liquid; adding a flocculating agent into the neutralization turbid liquid, and carrying out solid-liquid separation by a neutralization thickener to obtain a neutralization underflow and a neutralization overflow; and refluxing one part of the neutralization bottom flow to the neutralization reaction tank, and performing filter pressing dehydration treatment on the other part of the neutralization bottom flow to obtain second filter pressing residues and second filter pressing liquid.
As a further improvement of the present invention, in step S1, the concentration of copper ions in the iron-containing acidic water is not less than 370mg/L, and the pH is adjusted in such a manner that: adding a pH value regulator to regulate the pH value to 3.0-3.6, and reacting for 0.25-0.5 h; the pH value regulator is lime milk or carbide slag.
As a further improvement of the invention, in the step S1, when the mass ratio of copper ions to ferric ions in the iron-containing acidic water is less than 1:1.83, the pH is adjusted to 3.0-3.3; and when the mass ratio of the copper ions to the ferric ions in the ferrite-containing water is greater than 1:1.83, regulating the pH to 3.3-3.6.
As a further improvement of the present invention, in step S2, the way of adjusting the ORP value is: adding a vulcanizing agent to adjust the ORP value to 0-200 mv, and reacting for 0.25-0.5 h; the vulcanizing agent is one of sodium sulfide, sodium hydrosulfide and hydrogen sulfide gas.
As a further improvement of the present invention, in step S3, the manner of adjusting the pH is: adding a pH value regulator to regulate the pH value to 8.2-8.8, and reacting for 0.8-1.2 h; the pH value regulator is lime milk or carbide slag.
As a further improvement of the invention, in the step S3, when the oxidant is air, the gas-liquid volume ratio of the oxidant to the neutralization liquid is 1:4-5; when the oxidant is hydrogen peroxide, the mass ratio of the adding amount of the oxidant to ferrous ions in the neutralization solution is 0.60-6:1.
As a further improvement of the invention, in the step S2, 2% -10% of the vulcanization underflow is refluxed into the vulcanization reaction tank.
As a further improvement of the invention, in the step S2, the first press filtration slag is collected as copper slag, and the grade of copper in the copper slag is more than 15%.
As a further improvement of the invention, 70% -90% of the neutralization underflow is refluxed to the neutralization reaction tank in the step S3.
As a further improvement of the invention, in the step S2 and the step S3, the flocculating agent is a nonionic flocculating agent, and the adding amount of the flocculating agent in the step S2 is 1-5 g/m 3 The addition amount of the flocculant in the step S3 is 1-15 g/m 3 。
The beneficial effects of the invention are as follows:
1. according to the method for comprehensively treating the ferrous acid water, provided by the invention, aiming at the pollution endowment characteristics of the ferrous acid water rich in heavy metals, the water treatment process is reasonably designed in combination with the current acidic water treatment process characteristics, the ferrous acid water is subjected to iron removal pretreatment, copper sulfide recovery and neutralization treatment in sequence, and the iron removal turbid liquid is directly input into the copper sulfide recovery working section without flocculation during the iron removal pretreatment, and meanwhile, the neutralization overflow and filter pressing liquid obtained in the neutralization process are treated by using an oxidant, so that the neutralization overflow and filter pressing liquid can meet the discharge standard, and the deep purification of the ferrous acid water is realized. Based on the mode, the method provided by the invention does not produce dangerous wastes such as iron-removing slag, thereby greatly reducing the production of solid wastes, reducing the environmental risk of slag accumulation, effectively reducing valuable substance copper lost with the iron slag liquid phase, and further improving the copper recovery rate of the whole acid water treatment system.
2. The method for comprehensively treating the ferrite-containing water successfully solves the problem of large fluctuation of the quality of the acidic water by further regulating and controlling the pH value, the ORP value, the reflux ratio and other parameters in the treatment process, can efficiently treat the ferrite-containing water into a water body meeting the discharge standard by a simple process, can also meet the I-type requirement of common industrial solid waste by the neutralization slag generated in the neutralization treatment process, simultaneously avoids the generation of dangerous waste such as iron slag, realizes the efficient recovery of valuable substance copper, and can reach the requirement of copper concentrate products by the generated copper slag, thereby having higher utilization value.
3. The method for comprehensively treating the ferrite-containing water has the advantages of simple process, safe and reliable operation, common used medicament and low price, can treat the ferrite-containing water into a water body conforming to the emission standard, avoids the generation of iron slag, improves the recovery rate of copper, has obvious economic benefit, environmental benefit and social benefit, and provides a new thought for treating the ferrite-containing acidic water.
Drawings
FIG. 1 is a schematic process flow diagram of the method for comprehensive treatment of sour water containing iron provided in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a method for comprehensively treating ferrite-containing water, which comprises the following steps:
s1, inputting ferrite-containing water into an iron removal reaction tank, and adjusting the pH value to obtain an iron removal turbid liquid;
s2, inputting the deironing turbid liquid obtained in the step S1 into a vulcanization reaction tank, and adding a vulcanizing agent to adjust the ORP value to obtain a copper-collecting turbid liquid for vulcanization; adding a flocculating agent into the copper-collecting turbid liquid, and carrying out solid-liquid separation by a vulcanizing thickener to obtain vulcanizing underflow and vulcanizing overflow; one part of the vulcanization underflow flows back to the vulcanization reaction tank, and the other part of the vulcanization underflow is subjected to filter pressing and dehydration treatment to obtain first filter pressing residues and first filter pressing liquid; wherein the first press filtration residue can be sold as copper residue;
s3, inputting the vulcanization overflow obtained in the step S2 and the first filter pressing liquid into a neutralization reaction tank, adjusting the pH value, and simultaneously introducing an oxidant to fully react to obtain a neutralization turbid liquid; adding a flocculating agent into the neutralization turbid liquid, and carrying out solid-liquid separation by a neutralization thickener to obtain a neutralization underflow and a neutralization overflow; a part of the neutralization underflow flows back to the neutralization reaction tank, and a part of the neutralization underflow is subjected to filter pressing and dehydration treatment to obtain second filter pressing residues and second filter pressing liquid; wherein the neutralization overflow and the second filter pressing liquid meet the discharge standard, and can be discharged after reaching the standard; the second press residues have leached toxic substances and toxic substance contents meeting the requirements of general industrial solid wastes, and can be used as general industrial solid wastes for compliance storage.
More specifically, in step S1, the ferrite-containing water may contain several or all of pollutants of copper, iron, zinc, lead, arsenic, manganese, nickel, cadmium, chromium, beryllium, etc., wherein the copper ion concentration is not lower than 370mg/L; the pH is adjusted in the following way: adding a pH value regulator to regulate the pH value to 3.0-3.6, so that most harmful substances such as iron and the like are converted into sediment, and the reaction time is 0.25-0.5 h; the pH value regulator is lime milk or carbide slag.
The pH value control value is related to the proportion of copper ions and ferric ions in the iron-containing acidic water, and specifically, when the mass ratio of the copper ions to the ferric ions in the iron-containing acidic water is less than 1:1.83, the pH value is adjusted to 3.0-3.3; when the mass ratio of copper ions to ferric ions in the ferrite-containing water is greater than 1:1.83, regulating the pH to 3.3-3.6; the adjustment principle is that the pH value approaches 3.6 when the copper ion content is higher and the ferric ion content is lower, and the pH value approaches 3.0 otherwise.
In step S2, the ORP value is adjusted in the following manner: adding a vulcanizing agent to adjust the ORP value to 0-200 mv so as to enable heavy metal ions (mainly copper and the like) to carry out chemical precipitation, wherein the reaction time is 0.25-0.5 h; the vulcanizing agent is one of sodium sulfide, sodium hydrosulfide and hydrogen sulfide gas. When a part of the sulfidizing underflow flows back to the sulfidizing reaction tank, controlling the reflux ratio to be 2% -10%, so that the mass concentration of the solid phase in the sulfidizing underflow in the circulating treatment process is controlled to be 10% -20%, the treatment pressure of the sulfidizing underflow filter-pressing working section is reduced, and the grade of copper in the first filter-pressing slag is controlled to be more than 15%.
In step S3, the pH is adjusted by: adding a pH value regulator to regulate the pH value to 8.2-8.8, so that most harmful substances such as heavy metals (especially manganese) are converted into sediment, and the reaction time is 0.8-1.2 h; the pH value regulator is lime milk or carbide slag. The reaction time of the oxidant and the neutralization solution is about 1 h; the oxidant is air or hydrogen peroxide, and when the oxidant is air, the gas-liquid volume ratio of the oxidant to the neutralization solution is 1:4-5; when the oxidant is hydrogen peroxide, the mass ratio of the adding amount of the oxidant to ferrous ions in the neutralization solution is 0.60-6:1. When a part of the neutralization underflow flows back to the neutralization reaction tank, the reflux ratio is controlled to be 70% -90%, so that the mass concentration of the solid phase in the neutralization underflow in the circulating treatment process is controlled to be 15% -30%, and the treatment pressure of the subsequent working section is reduced.
In the steps, the flocculating agent is a nonionic flocculating agent, and the adding amount of the flocculating agent in S2 is 1-5 g/m 3 The addition amount of the flocculant in the step S3 is 1-15 g/m 3 。
The method for comprehensively treating the ferrite-containing water provided by the invention is described below with reference to specific examples.
Example 1
The embodiment provides a method for comprehensively treating ferrous acid-containing water, which aims at the situation that the ferrous acid-containing water contains high-concentration copper, iron and other heavy metals, wherein the copper concentration fluctuates in the range of 370.91-1225.36 mg/L, the iron concentration fluctuates in the range of 448.25-715.57 mg/L, the arsenic concentration is about 5mg/L and the manganese concentration is about 20mg/L, the schematic diagram of the process flow is shown in figure 1 (the dotted line in the figure represents underflow in a sludge state), and the method specifically comprises the following steps:
s1, removing iron
Inputting ferrite-containing water into an iron removal reaction tank, adding lime milk according to the mass ratio of copper ions to ferric ions in the ferrite-containing water, regulating the pH value to 3.5, so that heavy metal ions (mainly iron, arsenic and the like) are subjected to chemical precipitation, so that the heavy metal ions are removed through a solid form of heavy metal precipitation, reducing the concentration of the iron ions from 700 mg/L to about 200 mg/L after 0.5h of reaction, and obtaining iron removal turbid liquid, and entering a copper sulfide copper collecting section.
S2, copper is recovered by sulfuration
Inputting the deironing turbid liquid obtained in the step S1 into a vulcanization reaction tank, inputting 10% sodium bisulfide solution serving as a vulcanizing agent into the vulcanization reaction tank through a vulcanization slurry mixing tank, adjusting the ORP value to be 0-100 mv, and enabling heavy metal ions (mainly copper and the like) to carry out chemical precipitation, wherein the copper concentration in a liquid phase is below 0.5mg/L after the reaction for 0.5h, so as to obtain the copper-collecting turbid liquid. The copper-collecting turbid liquid is input into a vulcanization flocculation reaction tank according to the ratio of 2g/m 3 Adding a nonionic flocculant into the copper-receiving turbid liquid, then inputting the turbid liquid into a vulcanization sedimentation tank, and carrying out solid-liquid separation by a vulcanization thickener to obtain vulcanization overflow and vulcanization underflow in a sludge state; a part of the vulcanization underflow flows back to the vulcanization reaction tank through a vulcanization slurry mixing tank, and the reflux ratio is controlled to be 10%; the other part is subjected to filter pressing and dehydration treatment to obtain first filter pressing residues and first filter pressing liquid; wherein, the first filter press residue can be sold as copper slag (the copper grade is 18 percent, and the copper recovery rate is 99.1 percent); the first press filtrate and the sulfidation overflow enter a neutralization section.
S3, neutralization
And (2) inputting the vulcanization overflow and the first filter pressing liquid obtained in the step (S2) into a neutralization reaction tank, inputting lime milk into the neutralization reaction tank through a neutralization slurry mixing tank to adjust the pH value to about 8.5, simultaneously introducing air into the neutralization reaction tank, controlling the gas-liquid ratio to be 1:5, further oxidizing residual ferrous ions, and carrying out chemical precipitation on heavy metal ions (mainly iron, arsenic, zinc, lead, manganese, nickel and the like) so as to remove the solid forms precipitated by heavy metals, and obtaining a neutralization turbid liquid after reacting for 1 h. The neutralized turbid liquid is input into a neutralization flocculation reaction tank according to the proportion of 12g/m 3 Adding a nonionic flocculant into the neutralization turbid liquid, then inputting the mixture into a neutralization sedimentation tank, and carrying out solid-liquid separation by a neutralization thickener to obtain neutralization overflow and neutralization underflow in a sludge state; a part of the neutralization underflow flows back to the neutralization reaction tank through a neutralization slurry mixing tank, and the reflux ratio is controlled at 80The%; and (3) carrying out filter pressing dehydration treatment on one part to obtain second filter pressing residues and second filter pressing liquid. Wherein, the target heavy metals in the neutralization overflow and the second pressure filtrate meet the first-level emission standard of the integrated wastewater emission standard (GB 8978-1996) and the direct emission limit value requirement specified in the industrial pollutant emission standard of copper, cobalt and nickel (GB 25467-2010), and reach the standard of being discharged outside; the leaching toxicity and toxic substance content of the second filter press residue meet the requirements of general industrial solid waste, and can be used as general industrial solid waste for compliance storage.
The water quality of the water inlet and outlet of this example was measured, and the results are shown in the following table.
TABLE 1 Water quality of Inlet and outlet
| Project | pH | Cu | Pb | Zn | Mn |
| Acidic water containing iron | 2~4 | 370.91~1225.36 | 2.27 | 4.05~7.54 | 34~55.74 |
| Effluent quality | 8.51 | <0.16 | <0.01 | <0.04 | 1.04 |
| Integrated wastewater discharge Standard | 6~9 | 0.5 | 1.0 | 2.0 | 2.0 |
| Emission standard of industrial pollutants of copper, cobalt and nickel | 6~9 | 0.5 | 0.5 | 1.5 | - |
| Project | Ni | Be | Sulfate ion | Fe | |
| Acidic water containing iron | 4.36 | 0.026 | 11800~16200 | 448.25~715.57 | |
| Effluent quality | <0.03 | <0.00004 | 3200 | <0.12 | |
| Integrated wastewater discharge Standard | 1.0 | 0.005 | - | - | |
| Emission standard of industrial pollutants of copper, cobalt and nickel | 0.5 | - | - | - |
Note that: the pH value is dimensionless, and the rest index units in the table are mg/L.
Application example referring to the related requirements of hazardous waste identification Standard code (GB 5085.7-2019), the second filter pressing slag obtained in the step S3 is subjected to solid waste attribute pre-identification.
1) Flammability analysis
The pyrophoric substance is an article that is easily oxidized in air, emits heat, and burns itself. As can be seen from the definition, the main characteristic of the article is that the article can automatically generate heat and burn in the air. In the project, the main components of the second filter pressing slag are calcium sulfate and metal precipitate, and the second filter pressing slag is not inflammable after preliminary analysis.
2) Analysis of reactivity
The second filter pressing slag generated by the normal process of the project is stable at normal temperature and normal pressure and does not have explosive property, and does not change drastically under the condition of no detonation; at standard temperature and pressure (25 ℃,101.3 kPa), no detonation or explosive decomposition reaction occurred and the preliminary analysis was not explosive. The second filter press residue produced by the normal process of the project is contacted with water to generate no inflammable gas and little toxic gas, and can not generate toxic gas, steam or smoke which is enough to harm human health or environment when mixed with water, and can not decompose to generate hydrogen cyanide gas and H under the acidic condition 2 S gas. The second press filter residue does not belong to the waste oxidizing agent or the organic peroxide. Thus, the preliminary analysis is not reactive.
3) Primary analysis of acute toxicity
The main components of the second filter pressing slag generated by the normal process of the project are calcium sulfate and metal precipitate, and the second filter pressing slag is free from acute toxicity substances after preliminary analysis.
4) Corrosion analysis
And (3) preparing leaching liquid of the second filter pressing slag according to hazardous waste identification standard corrosiveness identification (GB 5085.1-2007), analyzing and testing, wherein the pH value of the leaching liquid of the second filter pressing slag is 7.7, the condition that the pH value is more than or equal to 12.5 or less than or equal to 2.0 is not met, and primarily analyzing that the second filter pressing slag is not corrosiveness.
5) Analysis of Leaching toxicity
The second press residues were subjected to toxicity leaching tests according to the requirements of the sulfate-nitric acid method (HJ/T299-2007) of the solid waste leaching toxicity leaching method, and the specific results are shown in Table 2.
TABLE 2 results of second press sludge Leaching toxicity analysis
| Index (I) | Hg | Hexavalent chromium ions | Cu | Mn | Zn |
| Second filter pressing slag | 0.14 | 0.004L | 0.63 | 0.174 | 57.5 |
| GB 5085.3-2007 Standard | 100 | 5×10 3 | 100 | - | 100×10 3 |
| Index (I) | Pb | Cd | Ni | Cr | Ba |
| Second filter pressing slag | 4.4 | 8.7 | 32.3 | 10.7 | 21.9 |
| GB 5085.3-2007 Standard | 5×10 3 | 1×10 3 | 5×10 3 | 15×10 3 | 100×10 3 |
| Index (I) | Be | As | Ag | Se | |
| Second filter pressing slag | 0.0007L | 2.2 | 10.0 | 8.3 | |
| GB 5085.3-2007 Standard | 20 | 5×10 3 | 5×10 3 | 1×10 3 |
Note that: cu and Mn are expressed in mg/L, the other index units are expressed in mug/L, and L represents a detection limit or lower.
As can be seen from the results of Table 2, the second press-filtered residue was preliminarily judged as a general industrial solid waste by comparing with "hazardous waste identification Standard leaching toxicity identification" (GB 5085.3-2007).
6) Toxic substance content
The second press sludge was subjected to component analysis according to the requirements of hazardous waste identification Standard toxic substance content identification (GB 5085.6-2007), and the specific results are shown in Table 3.
TABLE 3 analysis results of the second press sludge component
| Index (I) | Cu | As | Cd | Cr |
| Second filter pressing slag | 58500 | 26.9 | 7.7 | 6.3 |
| Index (I) | Pb | Zn | Mn | |
| Second filter pressing slag | 516 | 1110 | 3140 |
Note that: each index unit in Table 3 is "mg/kg".
The second filter pressing slag mainly comprises calcium sulfate and metal hydroxide precipitate, and the possible toxic substances in the second filter pressing slag are primarily judged to be arsenic acid and salt thereof and elemental manganese by comparing with hazardous waste identification standard toxic substance content identification (GB 5085.6-2007).
TABLE 4 analysis results of harmful substances of the second press filtration residue
| Sample of | Toxic substance name | Content (10) -6 ） | Conversion compounds | Content of Compound (10) -6 ) | Critical waste standard limit value |
| Second filter pressing slag | Arsenic (As) | 0.00269% | Calcium arsenate | 0.014275% | ≥0.1% |
| Second filter pressing slag | Manganese (Mn) | 0.314% | - | - | ≥3% |
As can be seen from Table 4, the toxic substance content of the second press-filtered residues is lower than the standard limit value of hazardous waste, and the standard requirements of general industrial solid waste are primarily judged to be met.
From the above results, it can be seen that the effluent quality and the generated solid waste meet the corresponding requirements after being treated by the method for comprehensive treatment of ferrite-containing water provided by the embodiment. And the treatment capacity of the whole treatment process to the ferrite-containing water reaches 400 and 400 m 3 And/h, the high-efficiency treatment of the iron-containing acidic water is realized, and the harmless effect of slag production is achieved.
Comparative examples 1 to 3
Comparative examples 1 to 3 respectively provide a method for comprehensive treatment of ferrite-containing water, and compared with example 1, the method is different in that the pH value in step S1, the ORP value in step S2 and the pH value in step S3 are respectively changed, corresponding parameters of each comparative example are shown in table 2, and other steps and parameters are the same as those of example 1, and are not described herein.
Table 5 Process parameters in comparative examples 1 to 3
| Comparative example | The pH value after the adjustment in the step S1 | ORP value after adjustment in step S2 | The pH value after the adjustment in the step S3 |
| Comparative example 1 | 4 | 100 | 8.5 |
| Comparative example 2 | 3.5 | 300 | 8.5 |
| Comparative example 3 | 3.5 | 100 | 7 |
After the ferrite-containing water was treated according to the method provided in comparative examples 1 to 3, the quality of the effluent water and the solid waste produced were detected, and the results are shown in Table 6.
Table 6A list of test results for comparative examples
| Comparative example | Copper grade of copper slag (%) | Copper recovery (%) | Effluent index |
| Comparative example 1 | 10.8 | 93.6 | Reaching the standard |
| Comparative example 2 | 21.2 | 86.2 | Reaching the standard |
| Comparative example 3 | 22.2 | 94.1 | Mn concentration is 5.2mg/L, exceeding standard |
As can be seen from Table 6, the pH value of the step S1 is controlled to be more than 3.6, the grade of copper in copper slag is directly affected, and the copper concentrate selling requirement (the copper grade is more than or equal to 15%) cannot be met; if the ORP value in the step S2 cannot be controlled below 200mv, the problem that copper in the acid water cannot be effectively recovered exists, the comprehensive recovery rate of copper in the comparative example 2 is only 86.2%, and the recovery rate is relatively low. In the step S3, if the pH value cannot be controlled to be about 8.5, the pH value cannot be controlled to ensure that each pollutant in the acidic water effectively meets the standard for treatment, particularly Mn, in a comparative example test, the concentration after treatment is still up to 5.2mg/L and is far higher than the limit value of 2mg/L required by the standard.
In summary, the invention provides a method for comprehensively treating ferrite-containing water. According to the method, iron-removing pretreatment, copper-collecting by vulcanization and neutralization treatment are sequentially carried out on ferrous water, iron-removing turbid liquid is directly input into a copper-collecting section by vulcanization without flocculation during the iron-removing pretreatment, and meanwhile, an oxidant is used for treatment during the neutralization process, so that neutralization overflow and filter-pressing liquid obtained during the neutralization process can meet the discharge standard, and deep purification of ferrous water is realized; the process does not produce de-ironing slag, greatly reduces the production of solid waste, effectively reduces valuable substance copper lost with the liquid phase of the iron slag, and further improves the copper recovery rate of the whole acid water treatment system. Through the mode, the invention can realize the effective treatment of the ferrite-containing water by using a simple process and a cheap and easily available medicament, the treated water body and the neutralized slag meet the corresponding discharge requirements, and the dangerous waste such as iron removal slag and the like is not generated, so that the invention has obvious economic benefit, environmental benefit and social benefit.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The comprehensive treatment method of the ferrite-containing water is characterized by comprising the following steps:
s1, inputting ferrite-containing water into an iron removal reaction tank, and adjusting the pH value to obtain an iron removal turbid liquid;
s2, inputting the deironing turbid liquid obtained in the step S1 into a vulcanization reaction tank, and adding a vulcanizing agent to adjust the ORP value to obtain a copper-collecting turbid liquid for vulcanization; adding a flocculating agent into the copper-collecting turbid liquid, and carrying out solid-liquid separation by a vulcanizing thickener to obtain vulcanizing underflow and vulcanizing overflow; refluxing one part of the sulfidizing underflow into the sulfidizing reaction tank, and performing filter pressing dehydration treatment on the other part of the sulfidizing underflow to obtain first filter pressing residues and first filter pressing liquid;
s3, inputting the vulcanization overflow obtained in the step S2 and the first filter pressing liquid into a neutralization reaction tank as neutralization liquid, adjusting the pH value, and simultaneously introducing an oxidant to fully react to obtain neutralization turbid liquid; adding a flocculating agent into the neutralization turbid liquid, and carrying out solid-liquid separation by a neutralization thickener to obtain a neutralization underflow and a neutralization overflow; and refluxing one part of the neutralization bottom flow to the neutralization reaction tank, and performing filter pressing dehydration treatment on the other part of the neutralization bottom flow to obtain second filter pressing residues and second filter pressing liquid.
2. The method for comprehensive treatment of ferrite-containing water according to claim 1, wherein the method comprises the following steps: in the step S1, the concentration of copper ions in the iron-containing acidic water is not lower than 370mg/L, and the pH is adjusted in the following way: adding a pH value regulator to regulate the pH value to 3.0-3.6, and reacting for 0.25-0.5 h; the pH value regulator is lime milk or carbide slag.
3. The method for comprehensive treatment of ferrite-containing water according to claim 2, wherein the method comprises the following steps: in the step S1, when the mass ratio of the copper ions to the ferric ions in the iron-containing acidic water is less than 1:1.83, the pH value is adjusted to 3.0-3.3; and when the mass ratio of the copper ions to the ferric ions in the ferrite-containing water is greater than 1:1.83, regulating the pH to 3.3-3.6.
4. The method for comprehensive treatment of ferrite-containing water according to claim 1, wherein the method comprises the following steps: in step S2, the ORP value is adjusted in the following manner: adding a vulcanizing agent to adjust the ORP value to 0-200 mv, and reacting for 0.25-0.5 h; the vulcanizing agent is one of sodium sulfide, sodium hydrosulfide and hydrogen sulfide gas.
5. The method for comprehensive treatment of ferrite-containing water according to claim 1, wherein the method comprises the following steps: in step S3, the pH is adjusted by: adding a pH value regulator to regulate the pH value to 8.2-8.8, and reacting for 0.8-1.2 h; the pH value regulator is lime milk or carbide slag.
6. The method for comprehensive treatment of ferrite-containing water according to claim 1, wherein the method comprises the following steps: in the step S3, when the oxidant is air, the gas-liquid volume ratio of the oxidant to the neutralization solution is 1:4-5; when the oxidant is hydrogen peroxide, the mass ratio of the adding amount of the oxidant to ferrous ions in the neutralization solution is 0.60-6:1.
7. The method for comprehensive treatment of ferrite-containing water according to claim 1, wherein the method comprises the following steps: in the step S2, 2% -10% of the sulfidation underflow is refluxed into the sulfidation reaction tank.
8. The method for comprehensive treatment of water containing ferrite according to claim 7, wherein: in the step S2, the first filter pressing slag is collected as copper slag, and the grade of copper in the copper slag reaches more than 15%.
9. The method for comprehensive treatment of ferrite-containing water according to claim 1, wherein the method comprises the following steps: in the step S3, 70% -90% of the neutralization underflow flows back to the neutralization reaction tank.
10. The method for comprehensive treatment of ferrite-containing water according to claim 1, wherein the method comprises the following steps: in the step S2 and the step S3, the flocculating agent is a nonionic flocculating agent, and the adding amount of the flocculating agent in the step S2 is 1-5 g/m 3 The addition amount of the flocculant in the step S3 is 1-15 g/m 3 。
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