CN111252875A - Treatment process of heavy metal-containing wastewater - Google Patents
Treatment process of heavy metal-containing wastewater Download PDFInfo
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- CN111252875A CN111252875A CN202010103925.4A CN202010103925A CN111252875A CN 111252875 A CN111252875 A CN 111252875A CN 202010103925 A CN202010103925 A CN 202010103925A CN 111252875 A CN111252875 A CN 111252875A
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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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The invention discloses a treatment process of heavy metal-containing wastewater, which comprises the following steps: 1) the modified kiln slag is obtained, and is specifically prepared by mixing kiln slag with a sodium hydroxide solution or a potassium hydroxide solution, wet-milling to make the granularity of the kiln slag-100 meshes, filtering, rinsing the filter slag with the sodium hydroxide solution or the potassium hydroxide solution until the content of zinc ions in the rinsing solution is less than or equal to 1mg/L, filtering, collecting the filter slag, and drying; 2) adding the modified kiln slag into the heavy metal-containing wastewater according to the standard that more than or equal to 13kg of modified kiln slag is added into each cubic piece of heavy metal-containing wastewater for adsorption and flocculation reaction; 3) and after the adsorption and flocculation reaction is finished, adjusting the pH value of the system to be 7-9, stirring for reacting for a certain time, and then performing sedimentation separation. The process has obvious effect of removing various heavy metal ions in the heavy metal-containing wastewater.
Description
Technical Field
The invention relates to treatment of industrial wastewater, in particular to a treatment process of wastewater containing heavy metals.
Background
With the continuous deepening of ecological environment construction, industrial wastewater reaches the standard and is discharged, thus becoming an important measure for protecting the environment of enterprises. In the nonferrous metallurgy industry, because of various types of nonferrous metals, poor and different raw materials, advanced and backward coexistence of metallurgy technology and different production scales, the sewage discharge amount and the water quality of a metallurgical plant are greatly different. The initial waste water after the non-ferrous metallurgical industrial factory area waste water scours factory area buildings and ground water, factory area washing waste water (dust removal, coal gas, flue gas and ground cleaning water), cooling water, slag flushing waste water, process waste water and the like can be separated according to the source. The waste water is mainly characterized by large water amount, various types, complex water quality, contained dangerous solid waste such as suspended particle slag sludge and the like, and various heavy metals contained in the dangerous solid waste, if the dangerous solid waste is not treated in time, the dangerous solid waste is leached and leaked by the waste water, and various heavy metals can be brought into surface water and underground water.
At present, the common treatment methods for the wastewater containing heavy metals in the metallurgical industry mainly comprise a chemical precipitation method, an oxidation-reduction method, an electrolysis method, a biological adsorption method, an ion exchange method and a membrane separation method. Some of the methods have huge construction investment funds, high later-stage process operation and maintenance cost, and require operators to have higher technical literacy and theoretical knowledge background, so that the method is not high in industrial applicability at present; some methods have the defects of laggard tradition, generation of a large amount of secondary solid waste residues, unstable operation and the like.
The technology of treating heavy metal wastewater by using slag has been reported in public, such as:
the invention with the publication number of CN103553197A discloses a method for removing arsenic in industrial wastewater by using smelting slagAdding acid into industrial wastewater containing more than 10mg/L of As and more than 10mg/L of Sb to adjust acidity, and controlling pH to be 0.5-4; adding smelting slag and oxidant to make the smelting slag and As in waste water under the condition of acid and oxidizing atmosphere3+、Sb3+Carrying out chemical reaction or physical adsorption, controlling the temperature to be 40-100 ℃, and carrying out heat preservation reaction for 1-3 h; adding a neutralizing agent for neutralization, and controlling the pH value to be 6-9; filtering the solution to obtain filtrate and filter residue, if the As content of the filtrate is less than 0.3mg/L and the Sb content is less than 0.5mg/L, removing impurities, sending the filtrate to a sewage treatment system to further purify other impurities, if the As content is more than 0.3mg/L and the Sb content is more than 0.5mg/L, repeating the steps until the filtrate is qualified, and sending the filter residue to a residue yard for stockpiling. According to the invention, smelting furnace slag is used for replacing a precipitator to remove impurities, and arsenic and antimony in the wastewater are rapidly and effectively removed within 1-3 h.
The invention patent with the publication number of CN109317084A discloses an adsorbent for adsorbing heavy metal cadmium ions by Osmant copper furnace slag and an adsorption method thereof, and specifically the adsorbent is obtained by preparing cooled Osmant furnace slag into 0.154mm tiny particles, cleaning, drying and grinding the cooled Osmant furnace slag to pass through a standard sieve of 100 meshes; and adding the adsorbent into the wastewater according to a corresponding proportion, oscillating for adsorption, standing, and filtering to separate the adsorbent from the wastewater. The invention can adsorb most of cadmium ions and has higher adsorption efficiency. Similar technical solutions are disclosed in patent publications CN109317085A and CN 109317086A.
Although the above inventions all have high adsorption efficiency, they have in common that: only one or two heavy metal ions can be removed independently, and no text or test shows that the heavy metal ions can be effectively adsorbed simultaneously. In addition, for similar invention patents with the publication number of CN109317084A and the like, although percentage data of reduction of cadmium ions exist, data of heavy metal ion content in wastewater do not exist, and the removal data cannot indicate whether the technical scheme is effective for removing cadmium from wastewater with high cadmium content; moreover, the removal data in the technical scheme is based on the experimental results of a laboratory, and the technical effect of the removal data in the practical production cannot be fully shown.
The kiln slag is produced in the technological process of preparing zinc hypoxide by using zinc-containing solid waste such as zinc-containing smoke dust, slag ash, gas ash and the like in steel plants as raw materials through a rotary kiln pyrogenic process enrichment. The kiln slag mainly contains iron, ferrite, carbon, a small amount of silicon dioxide, silicate, calcium oxide, aluminum oxide, sodium oxide and other chemical components, and is used as a common solid waste, and the kiln slag at present mainly comprises the following treatment methods: the iron ore concentrate is returned to an iron-making plant for blast furnace iron-making or sent to a non-ferrous metal smelting plant for alloy smelting, but the iron ore concentrate is unacceptable to the iron-making plant due to the fact that the iron ore concentrate contains unfavorable elements such as sulfur, phosphorus and the like, and can only be used as an additive in a proper amount; the tailings are mainly discarded in landfill, and part of the tailings are used for cement batching and roadbed landfill. At present, no relevant report that the modified kiln slag has good adsorption effect on various heavy metal ions in the heavy metal-containing wastewater is available.
Disclosure of Invention
The invention aims to solve the technical problem of providing a treatment process of heavy metal-containing wastewater, which has a remarkable removal effect on various heavy metal ions in the wastewater.
In order to solve the technical problems, the invention adopts the following technical scheme:
a treatment process of heavy metal-containing wastewater comprises the following steps:
1) the modified kiln slag is obtained, and is specifically prepared by mixing kiln slag with a sodium hydroxide solution or a potassium hydroxide solution, wet-milling to make the granularity of the kiln slag-100 meshes, filtering, rinsing the filter slag with the sodium hydroxide solution or the potassium hydroxide solution until the content of zinc ions in the rinsing solution is less than or equal to 1mg/L, filtering, collecting the filter slag, and drying;
2) adding the modified kiln slag into the heavy metal-containing wastewater according to the standard that more than or equal to 13kg of modified kiln slag is added into each cubic piece of heavy metal-containing wastewater for adsorption and flocculation reaction;
3) and after the adsorption and flocculation reaction is finished, adjusting the pH value of the system to be 7-9, stirring for reacting for a certain time, and then performing sedimentation separation.
In the technical scheme, the kiln slag is the rotary kiln slag generated in the process flow of preparing the zinc hypoxide by using zinc-containing solid wastes such as zinc-containing smoke dust, slag ash, gas ash and the like of a steel plant as raw materials through the fire enrichment of a rotary kiln. The heavy metal-containing wastewater refers to wastewater with the total content of heavy metal ions being less than or equal to 8000mg/L, and when the total content of heavy metal ions in the wastewater is more than 8000mg/L, the wastewater can be treated by adopting the conventional method so that the total content of heavy metal ions is less than or equal to 8000mg/L and then treated by using the technical scheme provided by the application. Specifically, the excessive wastewater can be diluted to meet the requirement, or an alkaline substance can be added into the excessive wastewater to adjust the pH value of the system to 9-10, and then chemical precipitation is carried out to remove part of heavy metal ions to meet the requirement. When the method of adding alkaline substances into the overproof waste water for chemical precipitation so as to enable the overproof waste water to meet the requirements is adopted, the pH value of a system is adjusted to be 7-9 by acid after adsorption and flocculation reaction are completed.
In the step 1) of the technical scheme of the invention, the concentration of the sodium hydroxide solution or the potassium hydroxide solution is greater than or equal to 0.5mol/L, and preferably 1-2 mol/L. When wet grinding is performed, the particle size of the kiln slag is preferably 150 to 250 mesh. In order to remove zinc ions in the kiln slag more quickly and better, rinsing is preferably performed under a heating condition, and more preferably at 50-70 ℃. The drying is preferably carried out at 100-120 ℃.
In the technical scheme of the invention, the feeding standard of the modified kiln furnace slag is preferably 15 kg-60 kg, and more preferably 15 kg-40 kg per cubic heavy metal-containing wastewater. The time for carrying out adsorption and flocculation reaction after the modified kiln slag is put in needs to be more than or equal to 30min, and the subsequent stirring reaction is combined for more than or equal to 30min, so that the indexes of the content of metal ions, the pH value and the like in the water body (the water sample is filtered or centrifuged and then is detected) can meet the national discharge standard (GB 8978 + 1996 Integrated wastewater discharge Standard). Preferably, the time of the adsorption and flocculation reaction is 40-60 min; the stirring reaction time is 40-60 min, and the stirring is preferably carried out by introducing air into a water body.
In the step 3) of the technical scheme of the invention, the pH value of the system is adjusted to 7-9 by adopting a conventional alkaline substance (such as an aqueous solution of sodium hydroxide, potassium hydroxide and the like) or an acid (such as hydrochloric acid, phosphoric acid and the like) according to needs.
According to the technical scheme, after the stirring reaction is finished, the indexes of the content of metal ions, the pH value and the like in the water body meet the national discharge standard, but the conventional sedimentation separation treatment is required before the discharge. The water after the stirring reaction can be sent into a settling tank for settling, and a flocculating agent with a conventional dosage (such as polyacrylamide and the like) can be added to improve the settling rate and effect, wherein the adding amount of the polyacrylamide is usually 0.01-10g/m3A body of water). After sedimentation treatment, supernatant liquor in the sedimentation tank can be discharged, and bottom layer slag slurry is treated according to the conventional method (such as pressure filtration and then is sent to a metallurgical plant for smelting and recycling of valuable metals).
Compared with the prior art, the invention has the beneficial effects that:
1. develops a method for applying the rotary kiln slag in the treatment of the wastewater containing the heavy metal, so that the kiln slag can realize the treatment of wastes with processes of wastes against one another, change wastes into valuables and recycle resources.
2. The kiln slag is modified, so that the modified kiln slag contains various components with high adsorption performance, such as carbon powder, porous microporous silicate, porous microporous silicon dioxide, ferrite, high-activity simple substance iron powder, porous microporous alumina, calcium oxide and the like; wherein the high-activity simple substance iron powder can replace various heavy metals and has a series of complex catalytic oxidation reactions with oxygen in the wastewater solution, and the Fe released by the reactions2+The mixed reaction tank also plays the role of an iron salt water treatment agent again, so that heavy metals can be removed, and the mixed reaction tank also has an obvious effect on removing total nitrogen, total phosphorus and COD; the carbon powder particles, the porous microporous silicate, the porous microporous silicon dioxide, the ferrite, the porous microporous alumina and the calcium oxide can play a role in high-efficiency adsorption or flocculation sedimentation;
3. the kiln slag modified by the method can simultaneously treat various heavy metal ions in the heavy metal-containing wastewater, including copper, zinc, nickel, cobalt, arsenic, silver, tin, lead, manganese, chromium, iron, mercury and the like, has the advantages of rapid separation, short flow, extremely obvious heavy metal removal effect, stable formed solid filter residue and difficult back dissolution in a dilute acid-alkali medium, and is particularly suitable for treating the heavy metal-containing wastewater generated in the process of producing the zinc sulfate monohydrate by using the zinc hypoxide through the processes of acid leaching, impurity removal, crystallization and the like; meanwhile, suspended matters, bacteria, viruses, algae, oil content, sulfur-containing organic matters and the like can be removed;
4. the method has the advantages of simple process, easy operation, low operation cost, environmental protection and easy industrialization.
Detailed Description
The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.
The kiln slag involved in the following embodiments is rotary kiln slag produced in a process flow of preparing zinc hypoxide by using zinc-containing solid wastes such as zinc-containing smoke dust, slag ash, gas ash and the like of a steel plant as raw materials through a rotary kiln pyrogenic process, and the component detection is shown in the following table 1.
Table 1:
| principal Components | Fe | C | SiO2 | Fe3O4 | FeO | FeS | Al2O3 | CaO | ZnO |
| Content/% | 38.73 | 10.14 | 14.67 | 4.91 | 15.26 | 0.84 | 5.13 | 5.69 | 1.43 |
The heavy metal-containing wastewater in the following embodiments is produced by using zinc-containing solid waste such as zinc-containing smoke dust, slag ash, gas ash and the like in a steel plant as a raw material by the applicant, enriching the zinc suboxide in a rotary kiln, and then carrying out acid leaching, impurity removal, crystallization and other processes on the zinc suboxide to produce zinc sulfate monohydrate, wherein the initial pH of the wastewater is 0.3-2.6.
Example 1
The total content of heavy metal ions in the wastewater containing heavy metals to be treated in this example is 9757mg/L, wherein the content of main heavy metal ions is shown in Table 2 below.
1) Mixing the kiln slag with 1mol/L sodium hydroxide solution (solid-liquid mass ratio is 1: 1.2) then wet grinding to make the particle size of the kiln slag-200 meshes, filtering, rinsing the filter residue with 1mol/L sodium hydroxide solution for multiple times (the solid-liquid mass ratio is 1: and rinsing is carried out at 50 ℃), until the content of zinc ions in the rinsing liquid is less than or equal to 1mg/L, filtering, collecting filter residues, and drying at 120 ℃ to obtain the modified kiln slag.
2) Because the total content of heavy metal ions in the wastewater containing heavy metal to be treated is more than 8000mg/L, the wastewater containing heavy metal needs to be treated so that the total content of heavy metal ions in the wastewater is less than 8000 mg/L. Pumping heavy metal-containing wastewater to be treated into a No. 1 mixing reaction tank, starting a Roots blower, carrying out air stirring on the wastewater to be treated in the No. 1 mixing reaction tank, adding a 15% sodium hydroxide solution into the tank to adjust the pH value of a system to be 9.8 for chemical precipitation, carrying out air stirring for 10min, then carrying out filter pressing, feeding filter residues into a heavy metal recovery process to recover heavy metals, injecting filtrate (wherein the total content of heavy metal ions is 93.27mg/L) into a No. 2 mixing reaction tank, starting a blower to carry out air stirring, and feeding the modified kiln slag obtained in the step 1) into the No. 2 mixing reaction tank according to the proportion of adding 25kg of modified kiln slag into each cubic volume of wastewater for adsorption and flocculation reaction for 40 min;
3) after completion of the adsorption and flocculation reaction (pH of the system was 10.4), the pH of the system was adjusted to 8.8 with 10% by volume hydrochloric acid, and the mixture was stirred with air for 60 min. After stirring, a water sample is collected and filtered, and the content and the pH value of heavy metal ions in the water sample are measured, and the measurement results are shown in the following table 3.
4) Sending the water body treated in the step 3) into an inclined tube sedimentation tank for sedimentation separation according to the proportion of 1g/m3Adding polyacrylamide to improve the sedimentation rate and effect, introducing supernatant into a rapid filter for filtering after sedimentation by an inclined tube, recycling or discharging the obtained clear water (the detection result of the obtained clear water is almost the same as that in the step 3) again), and carrying out filter pressing on the slag slurry at the bottom of the inclined tube sedimentation tank by a filter press, and delivering the filter slag to a metallurgical plant for smelting and recycling valuable metals.
Example 2
The total content of heavy metal ions in the heavy metal-containing wastewater to be treated in this example is 8049mg/L, wherein the content of main heavy metal ions is shown in table 2 below.
1) Mixing the kiln slag with 1.5mol/L sodium hydroxide solution (solid-liquid mass ratio of 1: 1.2) then wet grinding to make the particle size of the kiln slag-150 meshes, filtering, rinsing the filter residue with 1mol/L sodium hydroxide solution for multiple times (the solid-liquid mass ratio is 1: and rinsing at 60 ℃) until the content of zinc ions in the rinsing liquid is less than or equal to 1mg/L, filtering, collecting filter residues, and drying at 100 ℃ to obtain the modified kiln slag.
2) Because the total content of heavy metal ions in the wastewater containing heavy metal to be treated is more than 8000mg/L, the wastewater containing heavy metal needs to be treated so that the total content of heavy metal ions in the wastewater is less than 8000 mg/L. Pumping heavy metal-containing wastewater to be treated into a No. 1 mixing reaction tank, starting a Roots blower, carrying out air stirring on the wastewater to be treated in the No. 1 mixing reaction tank, adding a sodium carbonate solution with the mass fraction of 10% into the tank to adjust the pH value of a system to be 9.3 for chemical precipitation, carrying out pressure filtration after 5min of air stirring, sending filter residues into a heavy metal recovery process to recover heavy metals, injecting filtrate (wherein the total content of heavy metal ions is 97.16mg/L) into a No. 2 mixing reaction tank, starting a blower to carry out air stirring, and putting the modified kiln slag obtained in the step 1) into the No. 2 mixing reaction tank according to the proportion that 15kg of modified kiln slag is added into each cubic volume of wastewater for adsorption and flocculation reaction for 45 min;
3) after completion of the adsorption and flocculation reaction (pH of the system was 9.7), the pH of the system was adjusted to 8.1 with 10% by volume hydrochloric acid, and the mixture was stirred with air for 40 min. After stirring, a water sample is collected and filtered, and the content and the pH value of heavy metal ions in the water sample are measured, and the measurement results are shown in the following table 3.
4) Sending the water body treated in the step 3) into an inclined tube sedimentation tank for sedimentation separation, wherein the concentration is 5g/m3Adding polyacrylamide to improve the sedimentation rate and effect, introducing supernatant into a rapid filter for filtering after sedimentation by an inclined tube, recycling or discharging the obtained clear water (the detection result of the obtained clear water is almost the same as that in the step 3) again), and carrying out filter pressing on the slag slurry at the bottom of the inclined tube sedimentation tank by a filter press, and delivering the filter slag to a metallurgical plant for smelting and recycling valuable metals.
Example 3
The total content of heavy metal ions in the heavy metal-containing wastewater to be treated in this example is 6132mg/L, wherein the content of main heavy metal ions is shown in table 2 below.
1) Mixing the kiln slag with 0.5mol/L sodium hydroxide solution (solid-liquid mass ratio of 1: 1.5) and then wet grinding to ensure that the granularity of the kiln slag is-200 meshes, filtering, rinsing the filter residue for multiple times by using 0.5mol/L sodium hydroxide solution (the solid-liquid mass ratio is 1: and rinsing at 70 ℃) until the content of zinc ions in the rinsing liquid is less than or equal to 1mg/L, filtering, collecting filter residues, and drying at 100 ℃ to obtain the modified kiln slag.
2) Pumping the heavy metal-containing wastewater to be treated into a No. 2 mixed reaction tank, starting an air blower to stir air, and putting the modified kiln slag obtained in the step 1) into the No. 2 mixed reaction tank according to the proportion of adding 50kg of modified kiln slag into each cubic of wastewater for adsorption and flocculation reaction for 60 min;
3) after the adsorption and flocculation reaction was completed (pH of the system was 4.7), the pH of the system was adjusted to 6.8 with 15% by mass sodium hydroxide solution, and the mixture was stirred in air for 60 min. After stirring, a water sample is collected and filtered, and the content and the pH value of heavy metal ions in the water sample are measured, and the measurement results are shown in the following table 3.
4) Sending the water body treated in the step 3) into an inclined tube sedimentation tank for sedimentation separation according to the proportion of 10g/m3Adding polyacrylamide to improve the sedimentation rate and effect, introducing supernatant into a rapid filter for filtering after sedimentation by an inclined tube, recycling or discharging the obtained clear water (the detection result of the obtained clear water is almost the same as that in the step 3) again), and carrying out filter pressing on the slag slurry at the bottom of the inclined tube sedimentation tank by a filter press, and delivering the filter slag to a metallurgical plant for smelting and recycling valuable metals.
Example 4
The total content of heavy metal ions in the wastewater containing heavy metals to be treated in this example is 5847mg/L, wherein the content of main heavy metal ions is shown in table 2 below.
1) Mixing the kiln slag with 1mol/L sodium hydroxide solution (solid-liquid mass ratio is 1: 1) then wet grinding is carried out to ensure that the granularity of the kiln slag is-200 meshes, filtering is carried out, and filter residue is rinsed for multiple times by using 1.5mol/L sodium hydroxide solution (the solid-liquid mass ratio is 1: and rinsing is carried out at 70 ℃), until the content of zinc ions in the rinsing liquid is less than or equal to 1mg/L, filtering, collecting filter residues, and drying at 120 ℃ to obtain the modified kiln slag.
2) Pumping the heavy metal-containing wastewater to be treated into a No. 2 mixed reaction tank, starting an air blower to stir air, and putting the modified kiln slag obtained in the step 1) into the No. 2 mixed reaction tank according to the proportion of adding 45kg of modified kiln slag into each cubic of wastewater for adsorption and flocculation reaction for 60 min;
3) after the adsorption and flocculation reaction was completed (pH of the system was 4.5), the pH of the system was adjusted to 7.6 with 15% by mass sodium hydroxide solution, and the mixture was stirred in air for 50 min. After stirring, a water sample is collected and filtered, and the content and the pH value of heavy metal ions in the water sample are measured, and the measurement results are shown in the following table 3.
4) Sending the water body treated in the step 3) into an inclined tube sedimentation tank for sedimentation separation, wherein the concentration is 6g/m3Adding polyacrylamide to improve the sedimentation rate and effect, introducing supernatant into a rapid filter for filtering after sedimentation by an inclined tube, recycling or discharging the obtained clear water (the detection result of the obtained clear water is almost the same as that in the step 3) again), and carrying out filter pressing on the slag slurry at the bottom of the inclined tube sedimentation tank by a filter press, and delivering the filter slag to a metallurgical plant for smelting and recycling valuable metals.
Comparative example 4-1
The wastewater containing heavy metals to be treated in the comparative example is the same batch as the wastewater containing heavy metals to be treated in example 4, and the indexes are the same.
1) Pumping the heavy metal-containing wastewater to be treated into a No. 2 mixed reaction tank, starting an air blower to stir air, and putting the kiln slag into the No. 2 mixed reaction tank for adsorption and flocculation reaction for 60min according to the proportion that 45kg of the kiln slag is added into each cubic of wastewater (the kiln slag is not modified by a sodium hydroxide solution or a potassium hydroxide solution);
2) after the adsorption and flocculation reaction was completed (pH of the system was 3.5), the pH of the system was adjusted to 7.6 with 15% by mass sodium hydroxide solution, and the mixture was stirred in air for 50 min. After stirring, a water sample is collected and filtered, and the content and the pH value of heavy metal ions in the water sample are measured, and the measurement results are shown in the following table 3.
Comparative examples 4 to 2
The wastewater containing heavy metals to be treated in the comparative example is the same batch as the wastewater containing heavy metals to be treated in example 4, and the indexes are the same.
Example 4 was repeated, except that in step 2), the modified kiln slag was dosed at 12kg per cubic wastewater, with the remainder being unchanged.
After the stirring in step 3) is finished, collecting a water sample, filtering, and measuring the content of heavy metal ions and the pH value, wherein the measurement results are shown in the following table 3.
Table 2:
| example 1 | Example 2 | Example 3 | Example 4 | |
| PH | 2.6 | 2.1 | 0.8 | 0.3 |
| Zinc ion (mg/L) | 6613.22 | 5184.81 | 3936.10 | 4207.82 |
| Cadmium ion (mg/L) | 586.14 | 552.73 | 455.23 | 311.03 |
| Lead ion (mg/L) | 14.37 | 12.41 | 11.78 | 9.33 |
| Arsenic ion (mg/L) | 7.72 | 6.95 | 5.02 | 4.65 |
| Chromium ion (mg/L) | 776.40 | 716.62 | 539.54 | 406.24 |
| Nickel ion (mg/L) | 692.44 | 622.37 | 480.21 | 393.51 |
| Silver ion (mg/L) | 0.10 | 0.08 | 0.10 | 0.10 |
| Copper ion (mg/L) | 426.36 | 401.35 | 289.92 | 234.79 |
| Manganese ion (mg/L) | 640.59 | 551.62 | 414.05 | 279.48 |
| Mercury ion (mg/L) | 0.06 | 0.06 | 0.05 | 0.05 |
Table 3:
as can be seen from Table 3, after the wastewater containing heavy metals is treated by the process of the invention, the main pollution indexes of the purified water meet the national discharge standard of GB 8978 and 1996 Integrated wastewater discharge Standard, and the purified water can be directly discharged or recycled.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and modifications, and equivalents of some features of the invention, can be made without departing from the spirit and scope of the invention.
Claims (9)
1. A treatment process of heavy metal-containing wastewater comprises the following steps:
1) the modified kiln slag is obtained, and is specifically prepared by mixing kiln slag with a sodium hydroxide solution or a potassium hydroxide solution, wet-milling to make the granularity of the kiln slag-100 meshes, filtering, rinsing the filter slag with the sodium hydroxide solution or the potassium hydroxide solution until the content of zinc ions in the rinsing solution is less than or equal to 1mg/L, filtering, collecting the filter slag, and drying;
2) adding the modified kiln slag into the heavy metal-containing wastewater according to the standard that more than or equal to 13kg of modified kiln slag is added into each cubic piece of heavy metal-containing wastewater for adsorption and flocculation reaction;
3) and after the adsorption and flocculation reaction is finished, adjusting the pH value of the system to be 7-9, stirring for reacting for a certain time, and then performing sedimentation separation.
2. The process for treating wastewater containing heavy metals according to claim 1, wherein: the heavy metal-containing wastewater refers to wastewater with the total content of heavy metal ions less than or equal to 8000 mg/L.
3. The process for treating wastewater containing heavy metals according to claim 1, wherein: in the step 1), the concentration of the sodium hydroxide solution or the potassium hydroxide solution is more than or equal to 0.5 mol/L.
4. The process for treating wastewater containing heavy metals according to claim 1, wherein: in the step 1), rinsing is carried out at 50-70 ℃.
5. The process for treating wastewater containing heavy metals according to claim 1, wherein: in the step 2), the feeding standard of the modified kiln slag is that 15 kg-60 kg of the modified kiln slag is added into each cubic of heavy metal-containing wastewater.
6. The process for treating wastewater containing heavy metals according to claim 1, wherein: in the step 2), the time of the adsorption and flocculation reaction is more than or equal to 30 min.
7. The process for treating wastewater containing heavy metals according to claim 1, wherein: in the step 2), the time of the adsorption and flocculation reaction is 40-60 min.
8. The process for treating wastewater containing heavy metals according to claim 1, wherein: in the step 2), the stirring reaction time is more than or equal to 30 min.
9. The process for treating wastewater containing heavy metals according to claim 1, wherein: in the step 2), the stirring reaction time is 40-60 min.
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| CN112058211A (en) * | 2020-09-18 | 2020-12-11 | 昆明理工大学 | Method for processing methylene blue |
| CN114733479A (en) * | 2022-03-15 | 2022-07-12 | 合肥学院 | La2O3Preparation method and application of modified space furnace coarse slag filter cake porous adsorption material |
| CN115814565A (en) * | 2022-11-30 | 2023-03-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Potassium-sodium absorption method and absorbent for preparing vanadium-nitrogen alloy by pushed slab kiln calcination |
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| CN114733479B (en) * | 2022-03-15 | 2024-04-26 | 合肥学院 | La2O3Preparation method and application of modified spacecraft coarse slag filter cake porous adsorption material |
| CN115814565A (en) * | 2022-11-30 | 2023-03-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Potassium-sodium absorption method and absorbent for preparing vanadium-nitrogen alloy by pushed slab kiln calcination |
| CN115814565B (en) * | 2022-11-30 | 2024-05-31 | 攀钢集团攀枝花钢铁研究院有限公司 | Potassium-sodium absorption method and absorbent for preparing vanadium-nitrogen alloy by pushed slab kiln calcination |
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