CN110129061B - Stabilizer for repairing heavy metal pollution and preparation method and application thereof - Google Patents
Stabilizer for repairing heavy metal pollution and preparation method and application thereof Download PDFInfo
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- CN110129061B CN110129061B CN201910475540.8A CN201910475540A CN110129061B CN 110129061 B CN110129061 B CN 110129061B CN 201910475540 A CN201910475540 A CN 201910475540A CN 110129061 B CN110129061 B CN 110129061B
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Abstract
The invention relates to the technical field of heavy metal pollution remediation, in particular to a stabilizer for remedying heavy metal pollution, a preparation method and an application thereof, and the stabilizer comprises the following steps: a primary precipitation impurity removal step, namely adding an alkaline substance into the ferrous sulfate industrial waste liquid, controlling the pH of the waste liquid to be 5.0-6.0, and then removing suspended substances and large granular substances in the waste liquid through primary precipitation according to different sinking speeds to obtain an upper-layer waste liquid; secondary precipitation and impurity removal: adding a flocculating agent into the upper-layer waste liquid, uniformly stirring, and removing small granular substances in the waste liquid through secondary precipitation to obtain a supernatant; a neutralization and precipitation step, namely adding calcium alkaline substances into the supernatant, controlling the pH to 7.0-10.0, introducing air, neutralizing and precipitating, separating, collecting solid-phase precipitate, and washing to obtain precipitate; and a drying step, drying and grinding the precipitate to prepare the stabilizer, wherein the stabilizer has a long-term heavy metal repairing effect, high acid-base buffering capacity and a good adsorption effect.
Description
Technical Field
The invention relates to the technical field of heavy metal pollution remediation, in particular to a stabilizer for remedying heavy metal pollution and a preparation method and application thereof.
Background
Along with the rapid growth of population in China, the continuous expansion of industrial production scale and the rapid development of urbanization, the prevention and control of industrial waste water are more and more emphasized, the ferrous sulfate industrial waste liquid is a ferrous sulfate industrial waste liquid containing ferrous sulfate, waste acid and other impurities, a large amount of ferrous sulfate industrial waste liquid is generated in the processes of producing titanium dioxide by a sulfuric acid method and steelmaking by a rolling mill, wherein each ton of titanium dioxide products can generate 8-10 tons of waste water containing 150g/L of ferrous sulfate, in the past, the waste water is generally recovered by a vacuum evaporation or evaporation-free freezing crystallization method, the additional value of the recovered products is not high, the engineering investment is large, the equipment corrosion is strong, a few units are neutralized by lime, and the residual acid is discharged outside, so that the problems of environmental pollution and resource waste are not solved.
In recent years, a great deal of research has been carried out on the realization of the reuse of ferrous sulfate waste liquid by preparing iron oxide red or iron oxide black dye, although the dye products can reach the standard for use in the field of printing and dyeing, the research of applying the prepared product to the treatment of heavy metal pollution has not appeared, but the inventor also finds that when the iron oxide red or iron oxide black is applied to heavy metal pollution, the defects of poor repairing effect, poor long-term effect, soil pH change and soil hardening acceleration still exist, for example, Chinese patent document CN103145194A discloses a method for preparing iron oxide yellow by using ferrous sulfate as a titanium dioxide byproduct, comprising the refining, neutralization reaction, seed crystal preparation and oxidation synthesis of ferrous sulfate, wherein the method for controlling the pH value of the solution during the refining of the ferrous sulfate is adopted to effectively remove the impurities of manganese, magnesium and zinc, and in addition, the seed crystal preparation process is divided into the neutralization reaction process and the seed crystal preparation process, mixing Fe (OH)2The preparation process and the oxidation process of the suspension are separated, the shape of the seed crystal is effectively controlled to be in a shuttle shape or a needle shape, and the dispersibility of the seed crystal is improved.
The curing stabilization repair effect of the zero-valent iron and the ferric salt can reach more than 90 percent, but the cost is relatively high, the long-acting property is low, and the method is limited in large-scale engineering repair application. Therefore, a cheap and efficient iron-based stabilizing functional material is sought, and a brand-new medicament selection is provided for the future heavy metal stabilizing and repairing.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the soil pH is easy to change to accelerate soil hardening, secondary pollution is easy to cause, the long-acting property is poor or the cost is high in the prior art, so that the stabilizer for repairing heavy metal pollution, and the preparation method and the application thereof are provided.
The invention provides a preparation method of a stabilizer for repairing heavy metal pollution, which comprises the following steps:
a primary precipitation impurity removal step, namely adding an alkaline substance into the ferrous sulfate industrial waste liquid, controlling the pH of the waste liquid to be 5.0-6.0, and then removing suspended substances and large granular substances in the waste liquid through primary precipitation according to different sinking speeds to obtain an upper-layer waste liquid;
secondary precipitation and impurity removal: adding a flocculating agent into the upper-layer waste liquid, uniformly stirring, and removing small granular substances in the waste liquid through secondary precipitation to obtain a supernatant;
a neutralization and precipitation step, namely adding calcium alkaline substances into the supernatant, controlling the pH to 7.0-10.0, introducing air, neutralizing and precipitating, separating, collecting solid-phase precipitate, and washing to obtain precipitate;
and a drying step, drying and grinding the precipitate to obtain the stabilizer.
Further, the alkaline substance is one or more of calcium hydroxide, calcium carbonate, limestone, magnesium hydroxide, sodium hydroxide, magnesium carbonate and sodium carbonate.
Preferably, the calcium alkaline oxide is one or more of calcium hydroxide, calcium oxide and quicklime.
The invention also provides the stabilizer prepared by the method for repairing the heavy metal pollution.
Further, the stabilizer comprises 40-58% of ferric oxide and 13-25% of calcium sulfate by mass percent.
Preferably, the stabilizing agent also comprises silicon sulfate, zinc sulfate, aluminum sulfate and magnesium sulfate.
Further, the iron oxide is pebble-shaped micro-ceramic type low-crystallinity particles.
Preferably, the calcium sulfate is a rod-like crystalline particle.
The invention also provides a stabilizer prepared by the method for repairing heavy metal pollution, or an application of the stabilizer for repairing heavy metal pollution in repairing soil heavy metal pollution or removing water body heavy metal pollution.
Further, the heavy metal pollution is one or more of As, Cd, Pb, Cr (VI), Cu, Zn and Ni heavy metal pollution;
preferably, the heavy metal pollution is one or more of As, Pb, Cd and Cr (VI) polluted soil.
The preparation method of the stabilizer for repairing heavy metal pollution provided by the invention comprises the following steps:
primary precipitation and impurity removal: the method takes the ferrous sulfate industrial waste liquid as a raw material, and the ferrous sulfate industrial waste liquid is put into a quenching and tempering tank for pretreatment, so that the properties of the waste liquid, such as concentration, pH and the like, do not fluctuate in a large range in the subsequent chemical reaction process. Then, inputting the industrial waste liquid of the ferrous sulfate into a primary sedimentation tank, and adding limestone into the primary sedimentation tank until the pH value of the waste liquid is 5.0-6.0 so as to ensure that Cr contained in the waste liquid can be removed to the maximum extent3+Ions and simultaneously the ferrous ions can be maximally retained without precipitation reaction, and then the upper layer waste liquid is collected. The pH of the waste liquid is monitored on line in real time in the whole process, the dosage of limestone is adjusted in time to control the pH to be 5.0-6.0, the pH of the waste liquid is detected no less than four times every day, the industrial waste liquid completes one-time precipitation step in a primary precipitation tank, and most of particulate matters and Cr contained in the solution3+And removing ions in the primary sedimentation tank.
Secondary precipitation and impurity removal: adding a flocculating agent into the upper-layer waste liquid which still has certain turbidity and is obtained in the primary sedimentation tank, performing secondary sedimentation through an inclined plate sedimentation tank after stirring and mixing, outputting supernatant, controlling and outputting clear supernatant by visually observing the turbidity of the effluent, wherein the turbidity of a water outlet is not less than 8 times every day, the particle size of the supernatant is less than 10 mu m, and Cr in the process is3+The chromium-free chromium-.
And (3) a neutralization and precipitation step: and (3) conveying the supernatant obtained in the secondary precipitation impurity removal step into a reaction kettle, adding quicklime or caustic soda solution into the reaction kettle until the pH of the supernatant is 7.0-10.0, fully precipitating ferrous ions in the solution, continuously disturbing and blowing air to thoroughly oxidize the ferrous ions into ferric ions, reacting for 1-2 hours, filtering, collecting solid-phase precipitate, and washing the precipitate with clean water until the pH of a washing solution is 7.0-7.5.
And a drying step, namely placing the washed solid-phase precipitate into a reaction kettle, drying and aging at 100-150 ℃ for 8-12 h, and grinding to obtain the stabilizer.
According to the national standard GB/T7475-1987, the stabilizer for repairing heavy metal pollution provided by the invention is subjected to total chromium and hexavalent chromium content determination and hexavalent chromium leaching determination by adopting an atomic absorption photometry, wherein the total chromium content is lower than 20mg/kg, the hexavalent chromium content is lower than 10mg/kg, and the hexavalent chromium leaching content is lower than 0.05mg/kg, and all the requirements of the limit values of the national relevant standards are met.
Moreover, the stabilizing agent provided by the invention has the advantages of low crystallinity, large specific surface area, porosity and strong adsorption capacity, the iron oxide particles contained in the stabilizing agent have small particle size, are porous and loose, have low crystallinity and high reaction activity, can generate covalent chelation reaction with various specific heavy metal ions, and can be firmly adsorbed in a porous structure, and the stabilizing effect is better and more stable.
The technical scheme of the invention has the following advantages:
1. the preparation method of the stabilizer for repairing heavy metal pollution provided by the invention has the advantages of simple process flow and convenience in operation, and can retain Fe to the maximum extent by adopting the ferrous sulfate industrial waste liquid as a main raw material and carrying out a primary precipitation impurity removal step2+While removing a large amount of acid in the waste liquid and effectively removing Cr contained in the waste liquid3+、Al3+The metal ions are subjected to secondary precipitation and impurity removal, so that the aim of removing Fe is achieved2+Effective concentration of and on Cr3+The metal ions are further effectively removed, so that Cr is removed3+The removal rate of (A) is as high as 99.6%, so thatThe safety and the green environmental protection of the stabilizer are ensured, and then the pH is controlled to be 7.0-10.0 by adding calcium alkaline substances to ensure that Fe2+Precipitating completely and oxidizing completely under the condition of introducing air to obtain Fe (OH)3Precipitating and calcium sulfate precipitating, drying and grinding to obtain a micron-sized stabilizer with large surface area, wherein the main components of the stabilizer are iron oxide pebble-shaped micro-ceramic type low-crystallinity particles and calcium sulfate rod-shaped crystal particles, the pH value of the stabilizer is 7.5-8.5, the density of the stabilizer is 0.45-0.46 g/mL, the water content of the stabilizer is less than 3.0%, the specific surface area of the stabilizer is large and is 180m2More than g, the raw materials are easy to obtain, the price is low, the chemical property of the stabilizer is stable, the couplability is strong, the stabilization treatment on heavy metals can be realized through various modes such As covalent bond complexation, adsorption, coprecipitation and the like, so that the stabilizer not only has good adsorption effect on various heavy metals including As, Cd, Pb, Cr (VI), Cu, Hg, Zn and Ni, but also has long-term heavy metal restoration effect through long-term soil culture experiments, and the formation of calcium sulfate crystals can effectively prevent the microporous structure of iron oxide cluster charged ions from being blocked to influence the adsorption effect. In addition, the addition of the calcium sulfate can also improve the acid-base buffering capacity of the stabilizer, help the stabilizer to exert the optimal stabilizing effect in an environment with relatively neutral property, hardly cause the change of the pH value and chemical components of soil after application, belong to an environment-friendly green functional material, realize the recycling of the industrial waste liquid of the ferrous sulfate, effectively remove waste acid in the industrial waste liquid of the ferrous sulfate and change the industrial waste liquid of the ferrous sulfate into valuable.
2. According to the preparation method of the stabilizer for repairing heavy metal pollution, provided by the invention, the alkaline substance is added until the pH value of the ferrous sulfate industrial waste liquid is 5.0-6.0, so that Cr is obtained3+Fully precipitating to generate Cr (OH)3And the generation of iron precipitate is reduced as much as possible; and adding a calcium alkaline substance until the pH value of the ferrous sulfate industrial waste liquid is 7.0-10.0, so that Fe is fully precipitated.
3. According to the preparation method of the stabilizer for repairing heavy metal pollution, the drying temperature is controlled to be 100-150 ℃, the drying time is 8-12 hours, ferric oxide can be prevented from being crystallized and separated out, and ferric oxide cluster ions and a calcium sulfate rod-shaped crystal structure which are low in crystallization, large in surface area and in a micron-sized pore structure are effectively obtained.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a scanning electron microscope analysis chart of a stabilizer in example 1 of the present invention;
FIG. 2 is an EDX partial elemental analysis chart of the stabilizer in example 1 of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a preparation method of a stabilizer for repairing heavy metal pollution, which comprises the following steps:
(1) a primary neutralization and precipitation step: the method comprises the steps of taking ferrous sulfate industrial waste liquid with the ferrous sulfate concentration of 35g/L as a raw material, putting 100L of the ferrous sulfate industrial waste liquid into a conditioning and demodulation tank for pretreatment, inputting the ferrous sulfate industrial waste liquid into a primary sedimentation tank, and adding 21 into the primary sedimentation tank.43kg limestone until the pH of the waste stream is 5.0 to ensure maximum removal of Cr contained in the waste stream3+Ions and simultaneously the ferrous ions can be maximally retained without precipitation reaction, and then the upper layer waste liquid is collected. The pH of the waste liquid is monitored on line in real time in the whole process, the dosage of limestone is adjusted in time to control the pH to be 5.0-5.5, the pH of the waste liquid is detected no less than four times every day, the industrial waste liquid completes one-time precipitation step in a primary precipitation tank, and most of particulate matters and Cr contained in the solution3+And removing ions in the primary sedimentation tank.
(2) Secondary precipitation and impurity removal: adding 5g of polyaluminium chloride flocculant into the upper-layer waste liquid with certain turbidity, stirring and mixing for 30s, carrying out secondary precipitation step through an inclined plate sedimentation tank, outputting supernatant, controlling and outputting clear supernatant by visually observing the turbidity of outlet water, wherein the turbidity of a water outlet is not less than 8 times per day, the particle size of the supernatant is less than 10 microns, and Cr in the process is less than 10 microns3+The chromium-free chromium-;
(3) and (3) secondary neutralization and precipitation: and (3) conveying the supernatant obtained in the secondary precipitation impurity removal step into a reaction kettle, adding quicklime into the reaction kettle until the pH of the supernatant is 8.0, fully precipitating ferrous ions in the solution, continuously disturbing and blowing air to thoroughly oxidize the ferrous ions into ferric ions, reacting for 1 hour, filtering, collecting solid-phase precipitate, and washing the precipitate with clean water until the pH of a washing solution is 7.0.
(4) A drying and aging step: and (3) placing the washed solid-phase precipitate into a reaction kettle, drying and aging at 150 ℃ for 10h, and grinding to obtain the stabilizer.
Example 2
The embodiment provides a preparation method of a stabilizer for repairing heavy metal pollution, which comprises the following steps:
(1) a primary neutralization and precipitation step: taking ferrous sulfate industrial waste liquid with ferrous sulfate concentration of 45g/L as a raw material, and adding 100L of the ferrous sulfate industrial waste liquid into thermal refiningThe adjusting tank is used for pretreatment, so that the properties of the waste liquid such as concentration, pH and the like do not fluctuate in a large range in the subsequent chemical reaction process. Then, inputting the industrial waste liquid of the ferrous sulfate into a primary sedimentation tank, and adding 23.5kg of limestone into the primary sedimentation tank until the pH value of the waste liquid is 5.5 so as to ensure that Cr contained in the waste liquid can be removed to the maximum extent3+Ions and simultaneously the ferrous ions can be maximally retained without precipitation reaction, and then the upper layer waste liquid is collected. The pH of the waste liquid is monitored on line in real time in the whole process, the dosage of limestone is adjusted in time to control the pH to be 5.0-5.5, the pH of the waste liquid is detected no less than four times every day, the industrial waste liquid completes one-time precipitation step in a primary precipitation tank, and most of particulate matters and Cr contained in the solution3+And removing ions in the primary sedimentation tank.
(2) Secondary precipitation and impurity removal: adding 6g of polyaluminium chloride flocculant into the upper-layer waste liquid with certain turbidity, stirring and mixing for 100s, carrying out secondary precipitation step through an inclined plate sedimentation tank, outputting supernatant, controlling and outputting clear supernatant by visually observing the turbidity of outlet water, wherein the turbidity of a water outlet is not less than 8 times per day, the particle size of the supernatant is less than 10 mu m, and Cr in the process is less than 10 mu m3+The chromium-free chromium-;
(3) and (3) secondary neutralization and precipitation: and (3) conveying the supernatant obtained in the secondary precipitation impurity removal step into a reaction kettle, adding quicklime into the reaction kettle until the pH of the supernatant is 10.0, fully precipitating ferrous ions in the solution, continuously disturbing and blowing air to thoroughly oxidize the ferrous ions into ferric ions, reacting for 2 hours, filtering, collecting solid-phase precipitate, and washing the precipitate with clean water until the pH of a washing solution is 7.2.
(4) A drying and aging step: and (3) placing the washed solid-phase precipitate into a reaction kettle, drying and aging at 120 ℃ for 12h, and grinding to obtain the stabilizer.
Example 3
The embodiment provides a preparation method of a stabilizer for repairing heavy metal pollution, which comprises the following steps:
(1) a primary neutralization and precipitation step: the method is characterized in that ferrous sulfate industrial waste liquid with ferrous sulfate concentration of 55g/L is used as a raw material, 100L of the ferrous sulfate industrial waste liquid is put into a quenching and tempering tank for pretreatment, and the properties of the waste liquid such as concentration, pH and the like are ensured not to fluctuate in a large range in the subsequent chemical reaction process. Then, the industrial waste liquid of ferrous sulfate is input into a primary sedimentation tank, and 30kg of limestone is added into the primary sedimentation tank until the pH value of the waste liquid is 5.5, so as to ensure that Cr contained in the waste liquid can be removed to the maximum extent3+Ions and simultaneously the ferrous ions can be maximally retained without precipitation reaction, and then the upper layer waste liquid is collected. The pH of the waste liquid is monitored on line in real time in the whole process, the dosage of limestone is adjusted in time to control the pH to be 5.0-5.5, the pH of the waste liquid is detected no less than four times every day, the industrial waste liquid completes one-time precipitation step in a primary precipitation tank, and most of particulate matters and Cr contained in the solution3+And removing ions in the primary sedimentation tank.
(2) Secondary precipitation and impurity removal: adding 5g of polyaluminium chloride flocculant into the upper-layer waste liquid with certain turbidity, stirring and mixing for 50s, carrying out secondary precipitation step through an inclined plate sedimentation tank, outputting supernatant, controlling and outputting clear supernatant by visually observing the turbidity of outlet water, wherein the turbidity of a water outlet is not less than 8 times per day, the particle size of the supernatant is less than 10 microns, and Cr in the process is less than 10 microns3+The chromium-free chromium-;
(3) and (3) secondary neutralization and precipitation: and (3) conveying the supernatant obtained in the secondary precipitation impurity removal step into a reaction kettle, adding quicklime into the reaction kettle until the pH of the supernatant is 9.0, fully precipitating ferrous ions in the solution, continuously disturbing and blowing air to thoroughly oxidize the ferrous ions into ferric ions, reacting for 1 hour, filtering, collecting solid-phase precipitate, and washing the precipitate with clean water until the pH of a washing solution is 7.1.
(4) A drying and aging step: and (3) placing the washed solid-phase precipitate into a reaction kettle, drying and aging at 140 ℃ for 12h, and grinding to obtain the stabilizer.
Example 4
The embodiment provides a preparation method of a stabilizer for repairing heavy metal pollution, which comprises the following steps:
(1) a primary neutralization and precipitation step: the method is characterized in that ferrous sulfate industrial waste liquid with the ferrous sulfate concentration of 33g/L is used as a raw material, 100L of the ferrous sulfate industrial waste liquid is put into a quenching and tempering tank for pretreatment, and the properties of the waste liquid such as concentration, pH and the like are ensured not to fluctuate in a large range in the subsequent chemical reaction process. Then, the industrial waste liquid of ferrous sulfate is input into a primary sedimentation tank, 22kg of limestone is added into the primary sedimentation tank until the pH value of the waste liquid is 5.2, so as to ensure that Cr contained in the waste liquid can be removed to the maximum extent3+Ions and simultaneously the ferrous ions can be maximally retained without precipitation reaction, and then the upper layer waste liquid is collected. The pH of the waste liquid is monitored on line in real time in the whole process, the dosage of limestone is adjusted in time to control the pH to be 5.3-5.5, the pH of the waste liquid is detected no less than four times every day, the industrial waste liquid completes one-time precipitation step in a primary precipitation tank, and most of particulate matters and Cr contained in the solution3+And removing ions in the primary sedimentation tank.
(2) Secondary precipitation and impurity removal: adding 5g of polyaluminium chloride flocculant into the upper-layer waste liquid with certain turbidity, stirring and mixing for 30s, carrying out secondary precipitation step through an inclined plate sedimentation tank, outputting supernatant, controlling and outputting clear supernatant by visually observing the turbidity of outlet water, wherein the turbidity of a water outlet is not less than 8 times per day, the particle size of the supernatant is less than 10 microns, and Cr in the process is less than 10 microns3+The chromium-free chromium-;
(3) and (3) secondary neutralization and precipitation: and (3) conveying the supernatant obtained in the secondary precipitation impurity removal step into a reaction kettle, adding quicklime into the reaction kettle until the pH of the supernatant is 10.0, fully precipitating ferrous ions in the solution, continuously disturbing and blowing air to thoroughly oxidize the ferrous ions into ferric ions, reacting for 1 hour, filtering, collecting solid-phase precipitate, and washing the precipitate with clean water until the pH of a washing solution is 7.0.
(4) A drying and aging step: and (3) placing the washed solid-phase precipitate into a reaction kettle, drying and aging at 150 ℃ for 10h, and grinding to obtain the stabilizer.
Experimental example 1 basic Properties
The crystal structures of the stabilizers prepared in examples 1 to 3 and comparative example 1 were analyzed by a scanning electron microscope and an X-ray diffractometer.
As a result, it is understood that the stabilizers prepared in examples 1 to 3 are all composed of rod-like crystals and pebble-like microceramic crystals, wherein the rod-like crystals are calcium sulfate crystals, and the pebble-like microceramic crystals are iron oxide crystals.
Taking example 1 as an example, the elemental compositions of the stabilizers obtained by X-ray diffractometry measurement are shown in Table 1 below, and it is understood from Table 1 that the stabilizers mainly consist of Fe, Ca and S elements, and the bonding reaction mechanism shows that the stabilizer mainly contains Fe2O3·nH2O and CaSO4·nH2And O. And comparative example 1 had Fe as the main component2O3·nH2And O. Scanning electron microscope analysis, EDX local element analysis and XRD spectrum analysis are respectively carried out on the stabilizer prepared in example 1, as shown in figures 1 and 2, wherein in figure 1, A is a scanning electron microscope image under 300 times magnification, and B is a scanning electron microscope image under 7000 times magnification; in FIG. 2, A is total elements, B is Fe, C is Ca, and D is S.
TABLE 1 percentage of elements (%)
| Item | Fe2O3 | SO3 | CaO | MnO | MgO | SiO2 | Al2O3 | ZnO |
| Example 1 | 52％ | 21％ | 20.3％ | 4％ | 2％ | 0.5％ | 0.1％ | 0.1％ |
Experimental example 2 stabilizing effect on heavy metal contaminated soil
Taking the stabilizer prepared in example 1 as an example, 9kg of contaminated soil was prepared by using NaAsO2 as an arsenic source, CdCl2 as a cadmium source, K2Cr2O7 as a chromium source, Cu (NO3)2 as a copper source, NiCl2 as a nickel source, (CH3COO)2Pb as a lead source, and ZnSO4 as a zinc source. Weighing 9kg of clean soil, paving the clean soil in a tray, adding 1.8L of mixed solution with the As concentration of 5757mg/L, Cd concentration of 3717mg/L, Cr (VI) concentration of 70mg/L, Cu concentration of 4954mg/L, Ni concentration of 752mg/L, Pb concentration of 1118mg/L and the Zn concentration of 5491mg/L into the clean soil, covering the clean soil with preservative film, maintaining the clean soil for 20 days, air-drying, grinding and sieving the clean soil with a 20-mesh sieve for later use. The prepared contaminated soil is equally divided into three parts, the stabilizer prepared in example 1 is respectively added into the contaminated soil according to the non-adding and adding ratios of 1%, 2% and 3% (mass ratio), the mixture is uniformly mixed, the water content of the soil is adjusted to 75 wt% of the maximum water holding capacity, samples are taken after 14 days, the leaching concentration of the heavy metals in the soil samples after remediation is respectively measured by a sulfuric acid-nitric acid method, and the results are shown in the following table.
TABLE 2 test results of heavy Metal leaching concentration (μ g/l)
| Addition ratio of stabilizer | As | Cd | Cr(VI) | Cu | Ni | Pb | Zn |
| Is not added | 5757 | 3717 | 70 | 4954 | 752 | 1118 | 5491 |
| 1.0％ | 3275 | 3674 | 21 | 3004 | 680 | 419 | 5245 |
| 2.0％ | 1223 | 2632 | 12 | 2872 | 659 | 385 | 4189 |
| 3.0％ | 243 | 913 | 2 | 2383 | 582 | 243 | 3945 |
As can be seen from Table 2, the stabilizer prepared in example 1 has good adsorption effect on heavy metals such As As, Cd, Pb, Cr (VI), Cu, Zn, Ni and the like in soil, especially on soil polluted by As, Pb, Cd and Cr (VI), wherein the adsorption on As and Pb conforms to the Langmuir model, the maximum adsorption capacity on As is 25mg/g, the maximum adsorption capacity on Pb is 985mg/g, and the remediation effect on soil heavy metal pollution is positively correlated with the addition ratio of the stabilizer.
Experimental example 3 stabilizing effect on heavy metal-contaminated water body
As shown in the following table, As, Cd and Pb solutions with different concentrations were prepared As the contaminated water, the stabilizer prepared in example 1 was added to the contaminated water at a concentration of 1g/L, and then stirred for 2 hours, filtered, the filtrate was collected, and the heavy metal content was measured, with the results shown in the following table,
TABLE 3 test results of heavy Metal concentrations (μ g/l)
As can be seen from Table 3, the stabilizer prepared in example 1 has good adsorption effect on heavy metals such As As, Cd and Pb in water.
Experimental example 4 Long term efficacy examination
9kg of contaminated soil was prepared by using NaAsO2 as arsenic source and (CH3COO)2Pb as lead source. Weighing 10kg of clean soil, spreading the soil in a tray, adding 2L of mixed solution with 0.85mg/L of As concentration of 0.6mg/L, Pb into the soil, covering with preservative film, maintaining for 20 days, air-drying, grinding and sieving with a 20-mesh sieve for later use. The prepared contaminated soil was divided into 5 parts by weight, 3 wt% of each of the stabilizers prepared in example 1 was added, and the concentrations of Pb and As in the soil were measured for a period of time after each of the soil culture experiments for 654 days, and the results are shown in the following table.
TABLE 4 test results of heavy metal concentration in soil solution (. mu.g/l)
As can be seen from Table 4, the stabilizer prepared in example 1 of the present invention has good heavy metal stabilization and remediation effects during the soil culture experiment period of 654 days, and has long-term stability.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (11)
1. The preparation method of the stabilizer for repairing heavy metal pollution is characterized by comprising the following steps:
primary precipitation and impurity removal: adding an alkaline substance into the ferrous sulfate industrial waste liquid, controlling the pH of the waste liquid to be 5.0-6.0, and removing suspended matters and large-particle substances in the waste liquid through primary precipitation according to different sinking speeds to obtain an upper-layer waste liquid, wherein the alkaline substance is one or more of calcium hydroxide, calcium carbonate, limestone, magnesium hydroxide, sodium hydroxide, magnesium carbonate and sodium carbonate;
secondary precipitation and impurity removal: adding a flocculating agent into the upper-layer waste liquid, uniformly stirring, and removing small granular substances in the waste liquid through secondary precipitation to obtain a supernatant;
and (3) a neutralization and precipitation step: adding a calcium alkaline substance into the supernatant, controlling the pH to 7.0-10.0, introducing air, neutralizing the precipitate, separating, collecting the solid phase precipitate, and washing to obtain a precipitate;
and (3) drying: drying the precipitate, and grinding to obtain a stabilizer; wherein the drying temperature is 100-150 ℃, and the drying time is 8-12 h.
2. The method for preparing a stabilizer for remediating heavy metal pollution as recited in claim 1, wherein said calcium-based alkaline substance is one or more substances selected from the group consisting of calcium hydroxide, calcium oxide and quicklime.
3. The stabilizer prepared by the method for repairing heavy metal pollution according to claim 1 or 2.
4. The stabilizer for repairing heavy metal pollution according to claim 3, wherein the stabilizer comprises 40-58% by mass of ferric oxide and 13-25% by mass of calcium sulfate.
5. The stabilizer for remediating heavy metal pollution according to claim 4, wherein the stabilizer further comprises one or more of silicon sulfate, zinc sulfate, aluminum sulfate and magnesium sulfate.
6. A stabilizer for remediating heavy metal pollution as set forth in claim 4 or 5, wherein said iron oxide is pebble-like microceramic type crystal particles.
7. The stabilizer for remediating heavy metal pollution according to claim 4 or 5, wherein the calcium sulfate is a rod-like crystal particle.
8. The stabilizer for remediating heavy metal pollution according to claim 6, wherein the calcium sulfate is a rod-like crystal particle.
9. The application of the stabilizer for remedying heavy metal pollution of any one of claims 3 to 8 in remedying soil heavy metal pollution or removing water body heavy metal pollution.
10. Use according to claim 9, wherein the heavy metal contamination is As, Cd, Pb, Cr6+And one or more of heavy metal pollution of Cu, Zn and Ni.
11. Use according to claim 9, wherein the heavy metal contamination is As, Pb, Cd and Cr6+One or more of the above-mentioned substances are contaminated.
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| CN112759134B (en) * | 2021-01-04 | 2023-10-31 | 华东理工大学 | Recycling treatment method of coal chemical membrane filtration concentrated solution |
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| CN1193937C (en) * | 2001-03-13 | 2005-03-23 | 黄致祥 | Production process of high-purity ferric oxide for ferrite |
| CN1482069A (en) * | 2002-09-14 | 2004-03-17 | 熊育丰 | Process for preparing Fe hydroxide and oxide |
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