CN111517546A - Treatment method for recycling magnesium salt in copper-containing wastewater - Google Patents

Treatment method for recycling magnesium salt in copper-containing wastewater Download PDF

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CN111517546A
CN111517546A CN202010265075.8A CN202010265075A CN111517546A CN 111517546 A CN111517546 A CN 111517546A CN 202010265075 A CN202010265075 A CN 202010265075A CN 111517546 A CN111517546 A CN 111517546A
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wastewater
copper
treatment
precipitation
magnesium salts
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CN111517546B (en
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杨峰
戴建军
赵选英
程夫苓
刘君君
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Jiangsu Nanda Huaxing Environmental Protection Technology Co ltd
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    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5281Installations for water purification using chemical agents
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00Treatment of water, waste water, or sewage
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    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/727Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
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    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
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    • C02F2001/007Processes including a sedimentation step
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    • C02F2101/20Heavy metals or heavy metal compounds
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    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
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    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions

Abstract

The invention belongs to the technical field of water treatment, and relates to a treatment method for recovering magnesium salts from copper-containing wastewater. The invention provides a method for recovering magnesium salts in copper-containing wastewater, aiming at the problem that the recovered magnesium salts contain more miscellaneous salts due to the fact that a large amount of copper ions are contained in the high-concentration magnesium salt wastewater, firstly, aeration is carried out to convert monovalent copper into divalent copper, a metal complexing agent is used for precipitation to generate a copper complex, effluent is precipitated by sulfide, copper sulfide precipitation is separated out by stirring, effluent of the sulfide precipitation flows back to a metal complexing agent precipitation tank for secondary precipitation, copper is removed by copper removal resin adsorption of secondary precipitation effluent, the content of copper ions in the final effluent is low, the magnesium salts with high purity can be obtained by evaporation recovery, and the resin is regenerated by acid water to recover the copper ions.

Description

Treatment method for recycling magnesium salt in copper-containing wastewater
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a treatment method for recovering magnesium salts from copper-containing wastewater.
Background
Chemical enterprises can produce a large amount of high-salinity wastewater, and compared with other wastewater, the wastewater contains a large amount of inorganic salts. The wastewater is generally saturated saline water, and if the wastewater is discharged into the natural environment without being treated, the mineralization degree of the water quality of rivers can be directly improved, more and more serious pollution is brought to soil, surface water and underground water, and the ecological environment is endangered. The salt substances contained in the high-salinity wastewater are mostly Cl-、SO4 2-、Na+、PO4 +Although these ions are all essential nutrients for the growth of microorganisms, they play an important role in promoting enzyme reaction, maintaining membrane balance and regulating osmotic pressure during the growth of microorganisms, and if the concentration of these ions is too high, they will have inhibitory and toxic effects on microorganisms, thereby seriously affecting the purification effect of biological treatment systems. The main performance is as follows: the salt concentration is high, the osmotic pressure is high, and the microbial cells are dehydrated to cause cell protoplast separation; the salting-out action reduces the dehydrogenase activity; the chloride ions have toxic action on bacteria; the high salt concentration increases the density of the wastewater, and the activated sludge is easy to float and run off. Therefore, the high-salinity wastewater should be desalted. In the water treatment process, different treatment methods are selected according to different salinity concentrations, and when the salinity is more than 2000mg/L, evaporation concentration desalination is the most economical and effective feasible method. Other methods, such as the cultivation of halophilic bacteria, are difficult to operate in industrial practice. However, the waste water contains more miscellaneous salts, so that the salt produced by distillation is solid waste or dangerous waste. Therefore, the single salt with higher purity is obtained by distilling the waste water with single salt content after removing the salt, so that the salt obtained by distillation is sold or recycled to production as a byproduct, thereby avoiding the generation of a large amount of solid waste and embodying the principle of green economy.
The method for removing copper in wastewater is multiple, but a single method for treating copper ions has great limitations, such as mature chemical method process and low cost, but has the disadvantages of secondary pollution risk and poor effect of removing low-content heavy metal ions. Therefore, in the treatment of copper-containing wastewater, especially wastewater with higher copper ion content, a plurality of treatment process combinations are often selected for treatment.
The Chinese patent application with the application number of 201610208202.4 and the application date of 2016.04.05 discloses a copper-containing industrial wastewater treatment method through retrieval, wherein the copper-containing wastewater is added with alkali to adjust the pH value to 7-10 to generate copper hydroxide precipitate, then water-soluble sulfide is added, stirring is performed for crystallization, and finally agricultural and forestry waste is added for adsorption, solid residue is filtered and adsorbed, so that the wastewater with lower copper ion concentration can be obtained.
The high-concentration magnesium salt waste water contains a large amount of copper ions, but the waste water generally recovers magnesium salts with high purity as by-products. The method has the characteristics that a large amount of hydroxide precipitates are generated in the wastewater under a neutral condition, divalent copper ions with oxidability can be replaced by magnesium simple substances with strong reducibility, impurities cannot be introduced, and magnesium salts with higher purity can be obtained, but the magnesium simple substances used in the reaction have higher price to cause higher treatment cost, and a large amount of heat is released in the reaction process, and the reaction requirement is higher due to the need of cooling and the like. Therefore, in order to solve the above problems, it is necessary to provide a green and economical treatment method with good treatment effect and simple operation.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem that the prior high-concentration magnesium salt wastewater contains a large amount of copper ions and the recycled magnesium salt contains more miscellaneous salts, the invention provides a method for recycling the magnesium salt in the copper-containing wastewater.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention provides a treatment method for recovering magnesium salt from copper-containing wastewater, which comprises the following specific steps:
s100, introducing the wastewater into an aeration tank for aeration stirring;
s200, adjusting the pH of effluent in the S100 to 6-8, and adding a heavy metal complexing agent for complexing and stirring;
s300, introducing the effluent in the step S200 into a flocculation tank, and adding a flocculating agent to perform flocculation, precipitation and filtration in sequence;
s400, adding a precipitator into the effluent in the S300, stirring and precipitating, and filtering;
s500, refluxing the S400 effluent to S200, performing secondary precipitation, and entering S600 after the steps S300 and S400 are performed in sequence;
s600, introducing the effluent water in the S500 into a resin adsorption tower for resin adsorption;
s700, introducing the effluent in the S600 into an evaporator for evaporation to dryness to recover magnesium salts.
Preferably, one or more of air, oxygen or hydrogen peroxide is used for aeration in the aeration stirring.
Preferably, in the primary precipitation process, the heavy metal complexing agent is TMT-15, the dosage of the heavy metal complexing agent per kilogram of wastewater is a, the unit of a is g, the dosage of the precipitating agent per kilogram of wastewater is m, and the unit of m is g; in the reflux process of S500, the used heavy metal complexing agent is TMT-15, the adding amount of the heavy metal complexing agent in each kilogram of wastewater is b, the unit of b is g, the adding amount of the precipitator in each kilogram of wastewater is n, and the unit of n is g; b is 0.2a to 0.5a, and n is 0.2m to 0.5 m.
Preferably, the flocculant is one or both of PAC and PAM.
Preferably, the precipitant is one or two of potassium sulfide and sodium sulfide.
Preferably, the reflux ratio of the refluxed wastewater in S500 is 100%.
Preferably, the resin used for resin adsorption in S600 is a chelating resin, the resin adsorption capacity is 10-30 BV, and the resin adsorption rate is 1-4 BV/h.
Preferably, the resin adsorption in S600 includes a resin regeneration step, in which a regeneration solution first flows through the resin for elution to obtain a desorption solution; the regeneration liquid is an acid solution with the concentration of more than 10 percent.
Preferably, the evaporation recovery in S700 includes evaporation recovery or distillation recovery, and the evaporator used in the evaporation recovery is an MVR evaporator.
Preferably, in the primary precipitation process, the dosage of the heavy metal complexing agent in each kilogram of wastewater is 0.2-1.0 g, and the dosage of the precipitator in each kilogram of wastewater is 0.5-1 g; in the reflux process of S500, the dosage of the heavy metal complexing agent in each kilogram of wastewater is 0.1-0.5 g, and the dosage of the precipitator in each kilogram of wastewater is 0.2-0.5 g.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a treatment method for recovering magnesium salts from copper-containing wastewater, which comprises the steps of firstly aerating to convert monovalent copper into divalent copper, then utilizing a metal complexing agent to generate a copper complex, removing most copper ions, and then adopting a flocculation precipitation method to remove suspended matters; the effluent adopts sulfide, copper sulfide precipitate is separated out by stirring, and part of copper ions are removed; and then copper is removed by adopting copper removal resin adsorption, the content of copper ions in final effluent is low, magnesium salts with high purity can be obtained by distillation and recovery, and the problem of low purity of magnesium salts obtained by recovering copper-containing high-salinity wastewater is solved.
(2) The invention provides a treatment method for recovering magnesium salts from copper-containing wastewater, which adopts two-step precipitation and one-step resin adsorption to remove copper, adopts TMT-15 to remove most of copper ions in the first step, then adopts soluble sulfide to precipitate the copper ions, can further reduce the concentration of the copper ions in the wastewater, avoids introducing a large amount of inorganic ions to influence the purity of subsequent magnesium salt recovery, and provides possibility for the economy of copper ion adsorption by resin; and finally, resin adsorption is adopted to obtain the wastewater with lower copper content.
(3) The invention provides a treatment method for recovering magnesium salt from copper-containing wastewater, which adopts a mode of combining two-step precipitation with secondary precipitation to precipitate copper ions in the wastewater, wherein most of the copper ions can be removed by the primary precipitation, the residual sulfur ions in the sulfide precipitation in the primary precipitation can be reused by the secondary precipitation, and the addition amount of a precipitator can be obviously reduced by the two-step precipitation, so that the operation cost is greatly saved.
(4) The invention provides a treatment method for recovering magnesium salt from copper-containing wastewater, and the resin adsorption has the advantages of good stability, good adsorption effect, regeneration and reutilization, simple process, convenient operation, good economic benefit, recyclability of the copper after analysis and the like; the resin used for resin adsorption is D-402 resin, and the resin can not affect magnesium ions in the wastewater while adsorbing copper ions; moreover, the invention also comprises a resin regeneration step, and the acid solution with the concentration of more than 10 percent is used as the regeneration liquid to avoid the generation of precipitate.
(5) The invention provides a treatment method for recovering magnesium salt from copper-containing wastewater, which converts monovalent copper in the wastewater into divalent copper through aeration oxidation, has low aeration oxidation cost and easy operation, can obviously improve the removal effect of a copper complexing sedimentation agent on copper ions, and removes most of the copper ions.
Drawings
FIG. 1 is a process flow diagram of wastewater treatment according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments; moreover, the embodiments are not relatively independent, and can be combined with each other according to needs, so that a better effect is achieved. Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
According to the treatment method for recovering the magnesium salt from the copper-containing wastewater, the treated wastewater is the high-concentration magnesium salt copper-containing wastewater, the concentration of copper ions in the wastewater is 500-2000 mg/L, and the concentration of magnesium ions is 20000-100000 mg/L. The method comprises the following specific steps:
s100, introducing the wastewater into an aeration tank, and adding oxidizing agents such as air, oxygen or hydrogen peroxide and the like for aeration stirring; monovalent copper in the wastewater is converted into divalent copper, the aeration oxidation cost is low, the operation is easy, the copper ion removal effect of the copper complex settling agent can be obviously improved, and most of copper ions are removed; it is worth mentioning that the conversion of monovalent copper ions can be determined completely by iodometry and instrumental detection;
s200, adjusting the pH value of effluent in the S100 to 6-8, adding a heavy metal complexing agent for complexing and stirring, and removing most of copper ions; the heavy metal complexing agent used is TMT-15;
s300, introducing the effluent in the step S200 into a flocculation tank, and adding a flocculating agent to perform flocculation, precipitation and filtration in sequence; the flocculant used is one or two of PAC and PAM;
s400, adding a precipitator into the effluent water in the S300 for precipitation, stirring the precipitate and filtering; the used precipitator is soluble sulfide, such as sodium sulfide, potassium sulfide and the like, the addition amount of the precipitator in each kilogram of wastewater in the primary precipitator precipitation process is m, and the addition amount of the precipitator in each kilogram of wastewater in the secondary precipitator precipitation process is n, wherein n is 0.2-0.5 m; furthermore, in the process of one-time precipitating agent precipitation, the adding amount of the precipitating agent in each kilogram of wastewater is 0.5 g-1 g; in the process of secondary precipitant precipitation, the dosage of the precipitant in each kilogram of wastewater is 0.2g to 0.5 g;
s500, refluxing the S400 effluent to S200, performing secondary precipitation, sequentially performing the steps S300 and S400, and then entering S600, wherein the reflux ratio of the wastewater is 100%; the copper ions in the wastewater are precipitated by combining two-step precipitation with secondary precipitation, most of the copper ions can be removed by the primary precipitation, the residual sulfur ions in the sulfide precipitation in the primary precipitation are reused by the secondary precipitation, the addition amount of a precipitator can be obviously reduced by the secondary precipitation, and the operation cost is greatly saved; moreover, the concentration of copper ions in the wastewater can be further reduced, so that the influence on the purity of subsequent magnesium salt recovery caused by introducing a large amount of inorganic ions is avoided, and the possibility is provided for the economical efficiency of copper ion adsorption by resin; it is worth to be noted that the heavy metal complexing agent used in the primary precipitation, complexing and stirring is TMT-15, the dosage of the heavy metal complexing agent in each kilogram of wastewater is a, the heavy metal complexing agent used in the reflux process is TMT-15, and the dosage of the heavy metal complexing agent in each kilogram of wastewater is b, and then b is 0.2 a-0.5 a; furthermore, in the one-time precipitation complexing stirring, the adding amount of each kilogram of wastewater is 0.2g to 1.0 g; in the secondary precipitation complexing stirring, the adding amount of each kilogram of wastewater is 0.1 g-0.5 g;
s600, introducing the effluent water in the step S500 into a resin adsorption tower for resin adsorption, wherein the resin does not influence magnesium ions in the wastewater while adsorbing copper ions; the resin used is chelating resin, such as D-402 resin, the resin adsorption capacity is 10-30 BV, and the resin adsorption rate is 1-4 BV/h; moreover, the resin adsorption also comprises a resin regeneration step, wherein the regenerated liquid firstly flows through chelating resin for elution to obtain desorption liquid; the regeneration liquid is an acid solution with the concentration of more than 10 percent, such as a sulfuric acid solution;
s700, introducing the effluent in the S600 into an evaporator for evaporation to dryness to recover magnesium salts, wherein the used evaporator is an MRV evaporator; the recovery by evaporation may be an evaporation recovery or a distillation recovery as long as the effect of precipitating the magnesium salt is achieved, for example, two-effect evaporation, three-effect evaporation, four-effect evaporation, and the like.
It is worth to say that MVR distilled water enters a sewage station of a factory for further treatment, and the obtained magnesium salt is sold as a byproduct or recycled to production.
As shown in fig. 1, the embodiment provides a treatment method for recovering magnesium salts from copper-containing wastewater, which comprises the following specific steps:
s100, introducing the wastewater into an aeration tank, and introducing air into the aeration tank for aeration stirring;
s200, adjusting the pH of effluent in the S100 to 7, and adding a heavy metal complexing agent TMT-15 for complexing and stirring; the adding amount of the primary precipitate is 0.4g of the primary precipitate added in each kilogram of wastewater, and the adding amount of the secondary precipitate is 0.3g of the secondary precipitate added in each kilogram of wastewater;
s300, introducing the effluent in the step S200 into a flocculation tank, and adding a flocculating agent to perform flocculation, precipitation and filtration in sequence; the flocculant is PAC or PAM;
s400, adding a precipitator into the effluent water in the S300 for precipitation, stirring to separate out copper sulfide precipitate, and filtering after precipitation; the used precipitator is potassium sulfide, the dosage of the primary precipitation is 0.8g of the dosage of the primary precipitation in each kilogram of wastewater, and the dosage of the secondary precipitation is 0.3g of the dosage of the secondary precipitation in each kilogram of wastewater;
s500, refluxing the S400 effluent to S200, performing secondary precipitation, sequentially performing the steps S300 and S400, and then entering S600, wherein the reflux ratio of the wastewater is 100%;
s600, introducing the effluent in the S500 into a resin adsorption tower for resin adsorption, wherein the used resin is D-402 resin, the resin adsorption capacity is 10BV, and the resin adsorption rate is 2 BV/h; the used regeneration liquid is a sulfuric acid solution with the concentration of more than 10 percent;
s700, introducing effluent water in the S600 into an MVR evaporator, and performing reduced pressure distillation to recover magnesium salts; and evaporating water from the MVR to enter a sewage station of the plant area for further treatment.
The method removes copper ions, the treated object is the copper-containing wastewater of a certain high magnesium salt in Jiangsu, the process flow of the invention is shown in figure 1, and the contents of each component of the wastewater sample before and after treatment are shown in table 1.
TABLE 1 wastewater treatment Water quality index
Example 2
The basic content of this embodiment is different from that of embodiment 1 in that the specific steps are as follows:
s100, introducing the wastewater into an aeration tank, and introducing air into the aeration tank for aeration stirring;
s200, adjusting the pH of effluent in the S100 to 6, adding a heavy metal complexing agent TMT-15, and carrying out complexing stirring; the adding amount of the primary precipitate is 1.0g of the primary precipitate added in each kilogram of wastewater, and the adding amount of the secondary precipitate is 0.5g of the secondary precipitate added in each kilogram of wastewater;
s300, introducing the effluent in the step S200 into a flocculation tank, and adding a flocculating agent to perform flocculation, precipitation and filtration in sequence; the flocculant used was PAC;
s400, adding a precipitator into the effluent water in the S300 for precipitation, stirring to separate out copper sulfide precipitate, and filtering after precipitation; the used precipitator is sodium sulfide, the dosage of the primary precipitation is 1g of the primary precipitation added in each kilogram of wastewater, and the dosage of the secondary precipitation is 0.5g of the secondary precipitation added in each kilogram of wastewater;
s500, refluxing the S400 effluent to S200, performing secondary precipitation, sequentially performing the steps S300 and S400, and then entering S600, wherein the reflux ratio of the wastewater is 100%;
s600, introducing the effluent water in the S500 into a resin adsorption tower for resin adsorption, wherein the used resin is D-402 resin, the resin adsorption capacity is 20BV, and the resin adsorption rate is 1 BV/h; the used regeneration liquid is a sulfuric acid solution with the concentration of more than 10 percent;
s700, introducing the effluent water in the S600 into an MVR evaporator, decompressing, evaporating and recovering magnesium salts; and evaporating water from the MVR to enter a sewage station of the plant area for further treatment.
The method removes copper ions, the treated object is high-magnesium salt copper-containing wastewater from Jiangsu, the process flow of the method is shown in figure 1, and the content of each component of the wastewater sample before and after treatment is shown in table 2.
TABLE 2 wastewater treatment Water quality index
Example 3
The basic content of this embodiment is different from that of embodiment 1 in that the specific steps are as follows:
s100, introducing the wastewater into an aeration tank, and adding oxygen into the aeration tank for aeration stirring;
s200, adjusting the pH of effluent in the S100 to 8, and adding a heavy metal complexing agent TMT-15 for complexing and stirring; the adding amount of the primary precipitate is 0.2g of the primary precipitate added in each kilogram of wastewater, and the adding amount of the secondary precipitate is 0.1g of the secondary precipitate added in each kilogram of wastewater;
s300, introducing the effluent in the step S200 into a flocculation tank, and adding a flocculating agent to perform flocculation, precipitation and filtration in sequence; the flocculant used is PAM;
s400, adding a precipitator into the effluent water in the S300 for precipitation, stirring to separate out copper sulfide precipitate, and filtering after precipitation; the used precipitator is sodium sulfide, the dosage of the primary precipitation is 0.5g of the primary precipitation added in each kilogram of wastewater, and the dosage of the secondary precipitation is 0.2g of the secondary precipitation added in each kilogram of wastewater;
s500, refluxing the S400 effluent to S200, performing secondary precipitation, sequentially performing the steps S300 and S400, and then entering S600, wherein the reflux ratio of the wastewater is 100%;
s600, introducing the effluent water in the S500 into a resin adsorption tower for resin adsorption, wherein the used resin is D-402 resin, the resin adsorption capacity is 30BV, and the resin adsorption rate is 4 BV/h; the used regeneration liquid is a sulfuric acid solution with the concentration of more than 10 percent;
s700, introducing effluent water in the S600 into an MVR evaporator, and performing reduced pressure distillation to recover magnesium salts; and evaporating water from the MVR to enter a sewage station of the plant area for further treatment.
The method removes copper ions, the treated object is high-magnesium salt copper-containing wastewater from Jiangsu, the process flow of the method is shown in figure 1, and the content of each component of the wastewater sample before and after treatment is shown in table 3.
TABLE 3 wastewater treatment Water quality index
Comparative example 1
The basic content of this comparative example is different from example 1 only in that: the raw water is directly subjected to complexing precipitation without aeration or oxidation stirring. In this method, copper ions were removed, and the contents of each component in the wastewater samples before and after the treatment were as shown in Table 4 in the same manner as in example 1.
TABLE 4 wastewater treatment Water quality index
Because the D-402 resin only adsorbs bivalent copper ions, and copper ions in the raw water of the wastewater almost exist in the form of monovalent copper, the monovalent copper in the wastewater which is not aerated or oxidized and stirred cannot be subjected to resin adsorption to remove copper, so that the final effluent has high copper ion content.
Comparative example 2
The basic content of this comparative example is different from example 1 only in that: more TMT-15 is added for complexing precipitation, soluble sodium sulfide is not added, and copper ions are controlled to be adsorbed by resin. In this method, copper ions were removed, and the contents of each component in the wastewater samples before and after the treatment were as shown in Table 5 in the same manner as in example 1.
TABLE 5 wastewater treatment Water quality index
More TMT-15 is added for complex precipitation, soluble sodium sulfide is not added, although the same copper ion removal effect can be achieved, the excessive TMT-15 addition increases the organic sulfur ion content of the wastewater, the wastewater turns yellow, and finally the recycled magnesium salt is deep in chroma and cannot meet the requirement of industrial by-products.
Comparative example 3
The basic content of this comparative example is different from example 1 only in that: after the wastewater is aerated and oxidized, resin is adopted to adsorb and remove copper, and then secondary precipitation is adopted. In the method, copper ions are removed, the wastewater is treated in the same way as in example 1, and the content of each component of the wastewater sample before and after treatment is shown in Table 6.
TABLE 6 wastewater treatment quality index
The adsorption capacity of the resin is limited, the resin is quickly adsorbed and saturated due to excessive copper ions, the resin adsorbed water adopts secondary precipitation, and the removal of copper ions by complex precipitation and sulfide precipitation is limited, so that the concentration of the copper ions in the final effluent is higher.
While the present invention has been described in detail with reference to the embodiments, those skilled in the art will appreciate that various changes can be made in the specific parameters of the embodiments without departing from the spirit of the present invention, and that various specific embodiments can be made, which are common variations of the present invention and will not be described in detail herein.

Claims (10)

1. A treatment method for recovering magnesium salts from copper-containing wastewater is characterized by comprising the following specific steps:
s100, introducing the wastewater into an aeration tank for aeration stirring;
s200, adjusting the pH of effluent in the S100 to 6-8, and adding a heavy metal complexing agent for complexing and stirring;
s300, introducing the effluent in the step S200 into a flocculation tank, and adding a flocculating agent to perform flocculation, precipitation and filtration in sequence;
s400, adding a precipitator into the effluent in the S300, stirring and precipitating, and filtering;
s500, refluxing the S400 effluent to S200, performing secondary precipitation, and entering S600 after the steps S300 and S400 are performed in sequence;
s600, introducing the effluent water in the S500 into a resin adsorption tower for resin adsorption;
s700, introducing the effluent in the S600 into an evaporator for evaporation to dryness to recover magnesium salts.
2. The treatment method for recovering magnesium salts from copper-containing wastewater according to claim 1, characterized in that: and one or more of air, oxygen or hydrogen peroxide is used for aeration in the aeration stirring.
3. The treatment method for recovering magnesium salts from copper-containing wastewater according to claim 1, characterized in that: in the primary precipitation process, the used heavy metal complexing agent is TMT-15, the dosage of a in each kilogram of wastewater is a, the unit of a is g, the dosage of the precipitant in each kilogram of wastewater is m, and the unit of m is g; in the reflux process of S500, the used heavy metal complexing agent is TMT-15, the adding amount of the heavy metal complexing agent in each kilogram of wastewater is b, the unit of b is g, the adding amount of the precipitator in each kilogram of wastewater is n, and the unit of n is g; b is 0.2a to 0.5a, and n is 0.2m to 0.5 m.
4. The treatment method for recovering magnesium salts from copper-containing wastewater according to claim 1, characterized in that: the flocculant is one or two of PAC and PAM.
5. The treatment method for recovering magnesium salts from copper-containing wastewater according to claim 1, characterized in that: the precipitator is one or two of potassium sulfide and sodium sulfide.
6. The treatment method for recovering magnesium salts from copper-containing wastewater according to claim 1, characterized in that: the reflux ratio of the wastewater refluxed in S500 was 100%.
7. The treatment method for recovering magnesium salts from copper-containing wastewater according to claim 1, characterized in that: the resin used for resin adsorption in the S600 is chelating resin, the resin adsorption capacity is 10-30 BV, and the resin adsorption rate is 1-4 BV/h.
8. The treatment method for recovering magnesium salts from copper-containing wastewater according to claim 1, characterized in that: s600, resin adsorption comprises a resin regeneration step, wherein a regeneration liquid flows through resin for elution to obtain a desorption liquid; the regeneration liquid is an acid solution with the concentration of more than 10%.
9. The treatment method for recovering magnesium salts from copper-containing wastewater according to claim 1, characterized in that: and the evaporation recovery in the S700 comprises evaporation recovery or distillation recovery, and an evaporator used for evaporation recovery is an MVR evaporator.
10. The treatment method for recovering magnesium salts from copper-containing wastewater according to claim 1, characterized in that: in the primary precipitation process, the dosage of the heavy metal complexing agent in each kilogram of wastewater is 0.2-1.0 g, and the dosage of the precipitator in each kilogram of wastewater is 0.5-1 g; in the reflux process of S500, the dosage of the heavy metal complexing agent in each kilogram of wastewater is 0.1-0.5 g, and the dosage of the precipitator in each kilogram of wastewater is 0.2-0.5 g.
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