CN116040772B - Harmless treatment method for high-copper acidic water treatment slag - Google Patents
Harmless treatment method for high-copper acidic water treatment slag Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02F2101/203—Iron or iron compound
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- C02F2209/04—Oxidation reduction potential [ORP]
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Abstract
The invention provides a harmless treatment method for high-copper acidic water treatment slag, and relates to the technical field of water treatment. The method comprises the steps of sequentially carrying out iron removal, copper recovery by vulcanization, neutralization and iron slag innocent treatment on the high-copper acidic water, so that the target heavy metals in the neutralization overflow and press filtrate obtained in the neutralization process meet the discharge standard, and the high-efficiency treatment on the high-copper acidic water is realized; and meanwhile, the iron slag generated in the iron removal process is treated by utilizing neutralization underflow, vulcanizing liquid or neutralizing liquid generated in the high-copper acidic water treatment process, and the leaching toxicity and toxic substance content of the treated iron slag can meet the requirements of general industrial solid waste in a waste treatment mode, so that the purpose of harmless slag production is realized. Through the mode, the method can realize the effective treatment of the high-copper acidic water by using a simple process and a low-cost medicament, the treated water body and slag meet the corresponding emission requirements, and meanwhile, the recovery rate of copper is improved, so that the method has remarkable 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 harmless treatment method for high-copper acidic water treatment produced slag.
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, the treatment method commonly adopted at present is a fractional precipitation method, namely, the valuable substances copper is recovered by a vulcanization method, and then other heavy metals in the acidic water are removed by a lime neutralization method (HDS method). When the content of impurity metals such as iron in the acidic water is high, iron removal pretreatment is needed before copper is received in order to ensure the grade of copper slag in the copper receiving section. 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 metals such as copper, arsenic, beryllium and the like in the wastewater is relatively high, the indexes of leaching toxicity (copper exceeding standard) and toxic substance content (arsenic exceeding standard) of precipitate slag formed after adding a flocculating agent in the iron removal 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. Therefore, how to reasonably optimize the high-copper acid water treatment process and ensure that the precipitation slag generated in the water treatment process can meet the requirements of general industrial solid wastes is a research hot spot for the current high-copper acid water treatment.
In view of the above, there is a need to design an improved treatment method for treating and rendering harmless the slag of high-copper acidic water.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a treatment method for treating and harmlessly producing slag by using high-copper acid water, which adopts a physical and chemical combined treatment technology to treat waste by using waste generated in the treatment process of the high-copper acid water, reduces pollution indexes such as leaching toxicity and toxic substance content of precipitation slag in the treatment process of the high-copper acid water, ensures that the leaching toxicity and toxic substance content of the precipitation slag meet the requirements of general industrial solid waste, and realizes harmlessness of producing slag.
In order to achieve the aim, the invention provides a harmless treatment method for treating slag generated in high-copper acidic water treatment, which comprises the following steps:
s1, inputting high-copper acidic water into an iron removal reaction tank, and adjusting the pH value to obtain an iron removal turbid liquid; adding a flocculating agent into the deironing turbid liquid, performing solid-liquid separation by an deironing thickener to obtain deironing underflow and deironing overflow, and inputting at least part of the deironing underflow into a harmless treatment section;
s2, inputting the iron removal overflow 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; carrying out filter pressing dehydration treatment on at least part of the vulcanized 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, and obtaining a neutralization turbid liquid after regulating the pH value; 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; carrying out filter pressing dehydration treatment on at least part of the neutralization underflow to obtain second filter pressing residues and second filter pressing liquid;
s4, performing innocent treatment on the iron removal underflow input into the innocent treatment working section in the step S1 by utilizing at least one of the vulcanization overflow obtained in the step S2 or the neutralization underflow obtained in the step S3 or the neutralization overflow.
As a further improvement of the present invention, in step S4, the method of innocent treatment is as follows:
mixing the deironing underflow input into the harmless treatment section with the neutralization underflow obtained in the step S3 for 2-10 min according to the mass ratio of 1:1-2 to obtain a mixed solution; performing filter pressing dehydration treatment on the mixed solution to obtain third filter pressing residues and third filter pressing liquid; and the third filter pressing liquid is input into the vulcanization reaction tank.
As a further improvement of the present invention, in step S4, the method of innocent treatment is as follows:
mixing the iron removal underflow input into the harmless treatment working section with one of the vulcanization overflow obtained in the step S2 or the neutralization overflow obtained in the step S3 according to a mass ratio of 1:1-3, stirring and washing for 10-40 min, and then performing filter pressing and dehydration treatment to obtain fourth filter pressing residues and fourth filter pressing liquid; and the fourth filter pressing liquid is input into the vulcanization reaction tank.
As a further improvement of the present invention, in step S1, the copper ion concentration in the high copper acid water is not less than 500mg/L, and the pH is adjusted by: adding a pH value regulator to regulate the pH value to 3.3-3.6, and reacting for 0.25-0.5 h; the pH value regulator is lime or carbide slag.
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 be 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 or carbide slag.
As a further improvement of the invention, in the step S1, 2% -10% of the iron removal underflow is refluxed into the iron removal reaction tank.
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, 70% -90% of the neutralization underflow is refluxed to the neutralization reaction tank in the step S3.
As a further improvement of the present invention, in step S1, step S2 and step S3, the flocculant is a nonionic flocculant; the addition amount of the flocculating agent in the step S1 and 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. aiming at the pollution intrinsic characteristics of the high-copper acid water rich in heavy metals, the treatment method for treating the produced slag is combined with the technical characteristics of the current acid water treatment, and adopts a physical and chemical combined treatment technology, and the finally obtained neutralization overflow and target heavy metals in the second pressure filtrate meet the discharge standard by sequentially removing iron, vulcanizing and collecting copper and neutralizing and precipitating the high-copper acid water, so that the high-efficiency treatment of the high-copper acid water is realized; on the basis, the invention uses the neutralization underflow, the vulcanizing liquid or the neutralizing liquid generated in the high-copper acidic water treatment process to treat the iron slag generated in the iron removal process based on the principle of treating waste by waste, so that the leaching toxicity and the toxic substance content of the treated iron slag can meet the requirements of general industrial solid wastes, the problem of shortage of intermediate product storage places is solved, the environmental risk in storage is reduced, and the purpose of harmless slag production is realized.
2. According to the harmless treatment method for treating the produced slag of the high-copper acidic water, the parameters such as the pH value, the ORP value, the reflux ratio and the like in the treatment process are further regulated and controlled, so that the high-copper acidic water can be efficiently treated into the water body meeting the emission standard by a simple process. In addition, the invention can reduce valuable copper lost with the liquid phase of the iron slag while carrying out innocent treatment on the iron slag generated in the water treatment process, thereby improving the recovery rate of copper in the whole high-copper acidic water treatment process.
3. The harmless treatment method for the high-copper acid water treatment slag provided by the invention has the advantages of simple process, safe and reliable operation, common used medicament and low price, can treat the high-copper acid water into water bodies and solid wastes which meet the emission standard, improves the recovery rate of copper, has obvious economic benefit, environmental benefit and social benefit, and provides a new thought for treating the high-copper acid water.
Drawings
Fig. 1 is a schematic process flow diagram of a treatment method for innocuous treatment of high copper acid water treatment slag 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 harmless treatment method for high-copper acidic water treatment slag production, which comprises the following steps:
s1, inputting high-copper acidic water into an iron removal reaction tank, and adjusting the pH value to obtain an iron removal turbid liquid; adding a flocculating agent into the deironing turbid liquid, and obtaining deironing underflow and deironing overflow after solid-liquid separation of the deironing thickener; one part of the iron removal underflow flows back to the iron removal reaction tank, and the other part of the iron removal underflow is input into a harmless treatment working section for performing harmless treatment on iron slag;
s2, inputting the iron removal overflow 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, and obtaining a neutralization turbid liquid after regulating the pH value; 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 after a part of the neutralization underflow is subjected to filter pressing and dehydration treatment, second filter pressing residues and second filter pressing liquid are obtained, and a part of the neutralization underflow can be used for innocent treatment of iron slag; 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 sludge is stored as a general industrial solid waste.
S4, performing innocent treatment on the iron removal underflow input into the innocent treatment working section in the step S1 by utilizing at least one of the vulcanization overflow obtained in the step S2 or the neutralization underflow obtained in the step S3 or the neutralization overflow.
In step S4, there are two methods for the innocent treatment:
the method comprises the following steps: mixing the iron removal bottom flow input into the harmless treatment section with the neutralization bottom flow obtained in the step S3 for 2-10 min according to the mass ratio of 1:1-2, and then performing filter pressing dehydration treatment on the mixed liquid to obtain third filter pressing residues and third filter pressing liquid; the third press filtration liquid can be input into the vulcanization reaction tank for recycling, and the third press filtration liquid can be stored as general industrial solid waste.
Wherein the mass concentration of the solid phase in the iron removal bottom flow input into the harmless treatment working section is 10% -20%, and the mass concentration of the solid phase in the neutralization bottom flow is 10% -20%; the mixing proportion between the iron removal bottom flow and the neutralization bottom flow which are input into the harmless treatment working section is adjusted, so that the copper concentration in the liquid phase of the obtained mixed liquid is 200-300 mg/L; in the process, as the pH value is raised after mixing, part of copper forms precipitation slag in a precipitation form, the mixing time is controlled to be 2-10 min, and then the press filtration dehydration operation is carried out, so that the leaching toxicity and toxic substance content of the generated third press filtration slag can reach the requirements of common industrial solid waste, and the product can be stored in a compliance way.
The second method is as follows: mixing the iron removal underflow input into the harmless treatment working section with one of the vulcanization overflow obtained in the step S2 or the neutralization overflow obtained in the step S3 according to a mass ratio of 1:1-3, stirring and washing for 10-40 min, and then performing filter pressing and dehydration treatment to obtain fourth filter pressing residues and fourth filter pressing liquid; and the fourth filter pressing liquid is input into the vulcanization reaction tank. The leaching toxicity and toxic substance content of the fourth filter press residue meet the requirements of general industrial solid waste, and the fourth filter press residue can be used as general industrial solid waste for compliance storage.
More specifically, in step S1, the high copper acidic 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 less than 500mg/L; the pH is adjusted in the following way: adding a pH value regulator to regulate the pH value to 3.3-3.6, 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 or carbide slag. When a part of the iron removal underflow flows back to the iron removal reaction tank, the reflux ratio is controlled to be 2% -10%, so that the mass concentration of the solid phase in the iron removal underflow in the cyclic treatment process is controlled to be 15% -30%, and the innocent treatment pressure of the iron slag is reduced.
In step S2, the ORP value is adjusted in the following manner: adding a vulcanizing agent to adjust the ORP value to be 0-200 mv so as to enable heavy metal ions (mainly copper and the like) to be subjected to 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%, and the treatment pressure of the sulfidizing underflow filter pressing working section is reduced.
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 or carbide slag. 70% -90% of the neutralization underflow flows back to the reaction tank of the neutralization reaction tank to be vulcanized and overflowed, so that the mass concentration of the solid phase in the neutralization underflow in the cyclic treatment process is controlled to be 15% -30%, and the treatment pressure of the subsequent working section is reduced.
In the steps, the flocculating agents are nonionic flocculating agents, and the adding amount of the flocculating agents in the step S1 and 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 harmless treatment method for the high-copper acidic water treatment slag provided by the invention is described below by combining specific examples.
Example 1
The embodiment provides a harmless treatment method for high-copper acidic water treatment and slag production, which aims at the fact that high-copper acidic water contains heavy metals such as copper, iron and the like with higher concentration, wherein the copper concentration fluctuates within a range of 800-1200 mg/L, the iron concentration fluctuates within a range of 1000-2000 mg/L, the arsenic concentration is about 5mg/L, the manganese concentration is about 30mg/L, a process flow diagram is shown in figure 1, and (a dotted line in the figure represents underflow in a sludge state) specifically comprises the following steps:
s1, removing iron
And (3) buffering the high-copper acidic water by an adjusting buffer tank, inputting the high-copper acidic water into an iron removal reaction tank, inputting lime milk into the iron removal reaction tank by an iron removal slurry mixing tank, adjusting the pH value to 3.3-3.6, and carrying out chemical precipitation on heavy metal ions (mainly iron, arsenic and the like) so as to remove the heavy metal ions in a solid form through heavy metal precipitation, and reducing the concentration of the iron ions from about 2000mg/L to about 100mg/L after reacting for 0.5h to obtain an iron removal turbid liquid. The deironing turbid liquid is input into a deironing flocculation reaction tank according to the proportion of 2g/m 3 Adding a nonionic flocculant into the deironing turbid liquid, then inputting the solution into an deironing sedimentation tank, and carrying out solid-liquid separation by an deironing thickener to obtain deironing overflow and deironing underflow in a sludge state; a part of the iron removal underflow flows back to the iron removal reaction tank through an iron removal slurry mixing tank, and the reflux ratio is controlled to be 10%; the other part is input into a harmless treatment working section through an iron removal filter pressing buffer tank and is used for performing harmless treatment on iron slag; the iron removal overflow enters a copper sulfide recovery working section.
S2, copper is recovered by sulfuration
Inputting the iron removal overflow obtained in the step S1 into a vulcanization reaction tank, inputting 10% sodium bisulfide solution into the vulcanization reaction tank through a vulcanization slurry mixing tank as a vulcanizing agent, adjusting the ORP value to be 0-100 mv, carrying out chemical precipitation on heavy metal ions (mainly copper and the like), reacting for 0.5h, and obtaining copper-collecting turbid liquid after the copper concentration in a liquid phase is below 1 mg/L. The copper-collecting turbid liquid is input into a vulcanization flocculation reaction tank according to the following stepsAccording to 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 (copper grade is 60.2 percent, copper recovery rate is 94.5 percent); the first press filtrate and the sulfidation overflow enter a neutralization section.
S3, neutralization
And (2) inputting the vulcanization overflow obtained in the step (S2) and the first filter pressing liquid into a neutralization reaction tank, inputting lime milk into the neutralization reaction tank through a neutralization slurry mixing tank, and adjusting the pH value to about 8.5 to enable heavy metal ions (mainly iron, arsenic, zinc, lead, manganese, nickel and the like) to be subjected to chemical precipitation so as to be removed in a solid form of heavy metal precipitation, and reacting for 1h to obtain a neutralization turbid liquid. The neutralized turbid liquid is input into a neutralization sedimentation tank according to the weight of 12g/m 3 Adding a nonionic flocculant into the neutralization turbid liquid, and then carrying out solid-liquid separation by a neutralization thickener to obtain neutralization overflow and neutralization underflow in a sludge state; 80% of the neutralization underflow flows back to the neutralization reaction tank through a neutralization slurry mixing tank; after 10% of the neutralization bottom flow is subjected to filter pressing dehydration treatment, second filter pressing residues with the water content of about 50% and second filter pressing liquid are obtained; the rest part of the neutralization bottom flow is input into a harmless treatment working section through an iron removal filter pressing buffer tank and is used for performing harmless treatment on iron slag. 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 the discharge reaches the standard; 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.
S4, innocuous iron slag
The deironing underflow input into the innocent treatment working section in the step S1 is mixed with the neutralization underflow input into the innocent treatment working section in the step S3 in a deironing filter pressing buffer tank according to the mass ratio of 1:2; wherein, the mass concentration of the solid phase in the deironing underflow input into the harmless treatment working section is about 15 percent, and the concentration of copper in the liquid phase is about 800 mg/L; the mass concentration of the solid phase in the neutralization bottom flow is about 15%, and the concentration of copper in the liquid phase is below 0.5 mg/L; after the two are mixed, the pH value of the iron removal underflow is relatively raised, partial copper forms precipitation slag in a precipitation form, the reaction time is controlled to be 5 minutes, and the concentration of copper in the liquid phase of the obtained mixed solution is about 250 mg/L. Then, the mixed solution is input into an iron slag press filter to be subjected to press filtration and dehydration treatment, and third press filter residues and third press filter liquid with the water content of about 50% are obtained; the third filter pressing liquid is input into the vulcanization reaction tank for recycling, and the leaching toxicity and toxic substance content of the third filter pressing liquid reach the requirements of general industrial solid waste, so that the third filter pressing liquid 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 Table 1.
TABLE 1 acidic Water inlet and outlet Water quality Condition
Note that: the pH value is dimensionless, and the rest index units in the table are mg/L. pH, cu, pb, zn, cd, cr, as, ni, mn, COD, ammonia nitrogen and other indexes adopt the requirements of the first-level standard of the integrated wastewater discharge standard (GB 8979-1996), and sulfate adopts the table 2 standard of the surface water environment quality standard (GB 3838-2002).
The application example refers to the related requirements of hazardous waste identification Standard rule (GB 5085.7-2019), and the solid waste attribute pre-identification is carried out on the iron-removing slag (namely third filter pressing slag) obtained after the innocent treatment in the step S4, and the specific method is as follows.
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 third filter pressing slag are ferric hydroxide and metal precipitate, and the third filter pressing slag is not inflammable after preliminary analysis.
2) Analysis of reactivity
The third 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 third 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 is mixed with water to generate no toxic gas, steam or smoke which is enough to harm the health of human body or the environment, and the third filter press residue can not decompose to generate hydrogen cyanide gas and H under the acidic condition 2 S gas. The third 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 third filter pressing slag generated by the normal process of the project are ferric hydroxide and metal precipitate, and the primary analysis shows that the third filter pressing slag has no acute toxicity.
4) Corrosion analysis
And (3) preparing leaching liquid of the third 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 third filter pressing slag is 3.25, 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 third filter pressing slag has no corrosiveness.
5) Analysis of Leaching toxicity
The third press residues were subjected to toxicity leaching tests according to the requirements of sulfuric acid nitric acid method (HJ/T299-2007) for solid waste leaching toxicity leaching method, and the specific results are shown in Table 2.
TABLE 2 results of third press sludge Leaching toxicity analysis
Note that: in the table, hg unit is μg/L, the remaining index units are mg/L, and "L" indicates a detection limit or less.
As can be seen from the results of Table 2, the third 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 third press residue (third press residue) 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 third press sludge component
Note that: in the table, the index unit is mg/kg, and "L" indicates that the detection limit is less than or equal to the detection limit.
The third filter pressing slag mainly comprises ferric hydroxide and metal hydroxide precipitate, and the possible toxic substances in the third 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 in iron slag
As can be seen from Table 4, the contents of toxic substances in the iron-removing slag are lower than the standard limit value of hazardous waste, and the standard requirements of general industrial solid waste are primarily judged to be met.
Application example referring to the related requirements of hazardous waste identification Standard code (GB 5085.7-2019), the neutralization residue (namely second filter-pressing residue) obtained after neutralization in the step S3 is subjected to solid waste attribute pre-identification, and the specific method is as follows.
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 7.89, 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 solid waste leaching toxicity leaching method, and the specific results are shown in Table 5.
TABLE 5 results of second press sludge leaching toxicity analysis
Note that: in the table, the index unit is μg/L, and "L" indicates that the detection limit is less than or equal to the detection limit.
As can be seen from the results of Table 5, 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 6.
TABLE 6 analysis results of the second press sludge component
Note that: in the table, the index unit is mg/kg, and "L" indicates that the detection limit is less than or equal to the detection limit.
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 7 analysis results of harmful substances of the second press filtration residue
As can be seen from Table 7, 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 table, after the treatment method for treating the high-copper acid water treatment slag by using the harmless treatment method provided by the embodiment, the water quality of the effluent and the generated solid waste meet the corresponding requirements. And the treatment capacity of the whole treatment process to the high-copper acidic water reaches 500m 3 /h, harmless treatmentThe yield of the iron slag after the treatment is about 18t/d, so that the high-efficiency treatment of the high-copper 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 treatment method for innocuous treatment of high copper acid water treatment produced slag, and compared with example 1, the difference is that the pH value in step S1, the pH value in step S3 and the innocuous treatment process in step S4 are respectively changed, corresponding parameters of each comparative example are shown in Table 8, and other steps and parameters are the same as those of example 1, and are not repeated herein.
Table 8 Process parameters in comparative examples 1 to 3
After the high copper acid water was treated according to the method provided in comparative examples 1 to 3, the copper recovery rate, the effluent quality and the generated solid waste were detected, and the results are shown in table 9.
Table 9 test results in comparative examples 1 to 3
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As can be seen from table 9, in comparative example 1, controlling the pH value in step S1 to be 3.6 or more directly affects the recovery rate of copper in acidic water; in the comparative example 2, the related iron slag innocent treatment process of the step S4 is not adopted, the iron slag is directly subjected to pressure filtration without treatment, the copper concentration in the iron slag leaching poison leaching exceeds the standard, the property of the iron slag solid waste is dangerous waste, and the requirement of general industrial solid waste cannot be met; the pH value of the comparative example 3 in the step S3 is not controlled to be about 8.5, and the effective standard treatment of various pollutants in the acidic water, especially Mn, cannot be ensured, and the concentration of the treated pollutants still reaches 3.67 mg/L and is far higher than the limit value of 2mg/L required by the standard.
Examples 2 to 3
Embodiments 2 to 3 respectively provide a treatment method for harmless treatment of high-copper acidic water treatment produced slag, and compared with embodiment 1, the treatment method is different in that the harmless treatment method of iron slag in step S4 is changed, and the rest steps are consistent with embodiment 1, and are not repeated herein.
In example 2, the method for making iron slag harmless in step S4 comprises:
and (2) mixing the iron removal underflow input into the innocent treatment working section with the vulcanization overflow obtained in the step (S2) according to the mass ratio of 1:2, stirring and washing for 30min, and then performing filter pressing and dehydration treatment to obtain fourth filter pressing residues and fourth press filtrate.
The fourth press filtration liquid can be input into the vulcanization reaction tank for recycling, the leaching toxicity and toxic substance content of the fourth press filtration liquid are detected, the concentration of copper in the toxic leaching liquid is 55 mg/L and is lower than the standard limit value of 100mg/L, the concentration of other target pollutants meets the requirements, the requirements of general industrial solid waste are met, and the method can be used as general industrial solid waste for compliance storage.
In example 3, the iron removal underflow input into the innocent treatment section and the neutralization overflow obtained in the step S3 are mixed according to the mass ratio of 1:2, stirred and washed for 30min, and then subjected to filter pressing and dehydration treatment to obtain fourth filter pressing residues and fourth filter pressing liquid. The fourth filter pressing liquid obtained in the embodiment can be input into a vulcanization reaction tank for recycling, and the leaching toxicity and toxic substance content of the fourth filter pressing liquid are detected, wherein the concentration of copper in the toxic leaching liquid is 48 mg/L and is lower than the standard limit value of 100mg/L, and the concentration of other target pollutants meets the requirements, so that the requirements of general industrial solid waste are met, and the filter pressing liquid can be used as general industrial solid waste for compliance storage.
In conclusion, the invention provides a harmless treatment method for treating the slag produced by the high-copper acidic water. According to the method, the high-copper acidic water is sequentially subjected to iron removal, copper sulfide recovery, neutralization and iron slag innocent treatment, so that the target heavy metals in the neutralization overflow and press filtrate obtained in the neutralization process can meet the discharge standard, and the high-efficiency treatment of the high-copper acidic water is realized; the method can also treat the iron slag generated in the iron removal process by utilizing the neutralization underflow, the vulcanizing liquid or the neutralization liquid generated in the high-copper acidic water treatment process, and the leaching toxicity and the toxic substance content of the treated iron slag can meet the requirements of general industrial solid wastes in a waste treatment mode, so that the purpose of harmless slag production is realized. Through the mode, the method can realize the effective treatment of the high-copper acidic water by using a simple process and a cheap and easily available medicament, so that the treated water body and slag meet the corresponding emission requirements, and meanwhile, the recovery rate of copper is improved, and the method 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 (7)
1. The harmless treatment method for the high-copper acidic water treated slag is characterized by comprising the following steps of:
s1, inputting high-copper acidic water into an iron removal reaction tank, adding a pH value regulator to adjust the pH value to 3.3-3.6, and reacting for 0.25-0.5 h to obtain an iron removal turbid liquid; adding a flocculating agent into the deironing turbid liquid, performing solid-liquid separation by an deironing thickener to obtain deironing underflow and deironing overflow, and inputting at least part of the deironing underflow into a harmless treatment section; the concentration of copper ions in the high-copper acidic water is not lower than 500mg/L;
s2, inputting the iron removal overflow 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; carrying out filter pressing dehydration treatment on at least part of the vulcanized 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, adding a pH value regulator to adjust the pH value to 8.2-8.8, and reacting for 0.8-1.2 h 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; carrying out filter pressing dehydration treatment on at least part of the neutralization underflow to obtain second filter pressing residues and second filter pressing liquid;
s4, performing innocent treatment on the deironing underflow input into the innocent treatment working section in the step S1 by utilizing the neutralization underflow obtained in the step S3; the innocent treatment method comprises the following steps:
mixing the deironing underflow input into the harmless treatment working section with the neutralization underflow obtained in the step S3 for 2-10 min according to the mass ratio of 1:1-2 to obtain a mixed solution; performing filter pressing dehydration treatment on the mixed solution to obtain third filter pressing residues and third filter pressing liquid; the third filter pressing liquid is input into the vulcanization reaction tank; the mass concentration of the solid phase in the iron removal bottom flow input into the harmless treatment working section is 10% -20%, the mass concentration of the solid phase in the neutralization bottom flow is 10% -20%, and the copper concentration in the liquid phase of the mixed solution is 200-300 mg/L.
2. The harmless treatment method for the high-copper acidic water treatment slag, which is characterized by 1, comprises the following steps: the pH value regulator is lime or carbide slag.
3. The harmless treatment method for the high-copper acidic water treatment slag, which is characterized by 1, 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.
4. The harmless treatment method for the high-copper acidic water treatment slag, which is characterized by 1, comprises the following steps: in the step S1, 2% -10% of the iron removal underflow flows back to the iron removal reaction tank.
5. The harmless treatment method for the high-copper acidic water treatment slag, which is characterized by 1, comprises the following steps: in the step S2, 2% -10% of the sulfidation underflow is refluxed into the sulfidation reaction tank.
6. The harmless treatment method for the high-copper acidic water treatment slag, which is characterized by 1, comprises the following steps: in the step S3, 70% -90% of the neutralization underflow flows back to the neutralization reaction tank.
7. The harmless treatment method for the high-copper acidic water treatment slag, which is characterized by 1, comprises the following steps: in the step S1, the step S2 and the step S3, the flocculating agent is a nonionic flocculating agent; the addition amount of the flocculating agent in the step S1 and 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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