CN113461097A - Method for harmlessly treating hexavalent chromium ions by utilizing metallurgical desulfurization slag - Google Patents
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Abstract
The invention discloses a method for harmlessly treating hexavalent chromium ions by utilizing metallurgical desulfurization slag, which takes low-cost metallurgical solid waste as a raw material, adopts semi coke to modify the metallurgical desulfurization slag, and the modified metallurgical desulfurization slag has porous calcium silicate and calcium aluminum silicate. Compared with the prior art, the invention has the following advantages: (1) the method adopts the modified metallurgical desulfurization slag to achieve the highest absorption rate of hexavalent chromium ions, which can reach 86.7%; (2) the method not only solves the problem of environmental pollution caused by hexavalent chromium ions, but also greatly improves the comprehensive recovery utilization rate of metallurgical solid waste of iron and steel enterprises, and embodies a new environmental management concept of treating waste with waste; (3) the method is hardly affected by temperature, and good adsorption efficiency can be achieved under the room temperature condition in any season.
Description
Technical Field
The invention belongs to the technical field of environmental engineering, relates to a comprehensive recycling technology of metallurgical solid wastes and a harmless treatment technology of hexavalent chromium ions, and particularly relates to a method for harmlessly treating hexavalent chromium ions by utilizing metallurgical desulfurization slag.
Background
Hexavalent chromium is an inhalation toxicant and a swallow toxicant, and skin contact may cause allergy; more likely to cause genetic defects, inhalation may be carcinogenic, and there is a persistent risk to the environment. Hexavalent chromium is readily absorbed by the body and can invade the body through the digestive, respiratory, skin and mucous membranes. When the nasal mucosa is invaded by breathing, the nasal mucosa can be atrophied to different degrees, and the nasal septum can be perforated and the bronchus can be expanded when the nasal mucosa is serious. Vomiting and abdominal pain may occur when entering through the digestive tract. Dermatitis and eczema are produced by skin invasion. The most harmful is the carcinogenic danger of long-term or short-term contact or inhalation.
Hexavalent chromium ions mainly come from chromium slag and stainless steel pickling waste liquid, and harmful components in the chromium slag mainly include soluble sodium chromate, acid-soluble calcium chromate and other hexavalent chromium ions. About 30-50 million tons of sludge rich in hexavalent chromium ions are discharged in domestic metallurgical and chemical industries every year, and when the sludge is stockpiled in the open air, a large amount of hexavalent chromium ions are dissolved, lost and seeped into the earth surface along with rainwater after being washed and showered by the rainwater for a long time, so that underground water is polluted, rivers and lakes are polluted, and further, farmlands, aquatic products and human health are damaged.
There are many methods reported for treating wastewater containing hexavalent chromium ions, including chemical, physical and biological methods. These methods have advantages and disadvantages and are applicable to different conditions. In consideration of the preparation of raw materials and the convenience of operation, the adsorption method is widely applied due to the characteristics of wide application range, simple and convenient operation and metal recycling. Adsorption is a common method in environmental processes, where the adsorbent plays the most critical role. The cost of effective treatment of hexavalent chromium ions at the present stage is generally high, which can place a heavy burden on normal industrial production activities. Therefore, the research and development of the high-efficiency and low-cost adsorbing material for treating the hexavalent chromium ions in the wastewater becomes one of the current hot spots.
The molten iron pretreatment metallurgical desulfurization slag (metallurgical desulfurization slag for short) is an industrial solid waste resource, and steel mills in China produce about 1000 million tons of metallurgical desulfurization slag every year. The metallurgical desulfurization slag mainly comprises magnesium oxide, silicon dioxide, calcium oxide, calcium silicate, calcium aluminum silicate and the like, and due to the insufficient understanding of people on the metallurgical desulfurization slag, the existing treatment method of the metallurgical desulfurization slag comprises the following steps: the residual tailings after recovering the metallic iron from the desulfurization are discarded, and the discarded metallurgical desulfurization slag is not well utilized due to no advanced treatment technology, so that a large amount of metallurgical desulfurization slag is accumulated, which not only causes resource waste, but also occupies a large amount of land, and therefore, the search for a high-efficiency and high-valued method for treating the metallurgical desulfurization slag is urgent.
The metallurgical desulfurization slag is generally slag formed after steel making and iron making, and is mainly used for low-end applications such as paving at present. Particularly, the slag formed after smelting the laterite-nickel ore is about 5000 ten thousand tons generated in 2019 years in China, a large amount of slag cannot be processed to cause seawater and yard pollution, and the laterite-nickel ore slag is the second largest solid waste pollutant of the red mud which is only second to aluminum metallurgy generated at present.
Disclosure of Invention
The technical problem to be solved is as follows: in order to overcome the defects of the prior art, the method combines two environmental pollutants of metallurgical desulfurization slag and hexavalent chromium ions together to generate a physical and chemical reaction, thereby achieving the purposes of recycling wastes and efficiently treating the hexavalent chromium ions in the wastewater. In view of the above, the present invention provides a method for the harmless treatment of hexavalent chromium ions using metallurgical desulfurization slag.
The technical scheme is as follows: a method for the non-hazardous treatment of hexavalent chromium ions using metallurgical desulphurised slag, the method comprising the steps of:
s1, crushing the metallurgical desulfurization slag, carrying out reverse magnetic separation, ball milling and screening until the granularity is less than 100 meshes, and obtaining fine powder of the metallurgical desulfurization slag after iron removal;
s2, selecting semi-coke as a metallurgical desulfurization slag modifier, mixing the semi-coke with the doping amount of 1-40%, tabletting and re-sintering, wherein the sintering temperature is 800-1000 ℃;
s3, putting the metallurgical desulfurization slag modified by the S2 into wastewater containing hexavalent chromium ions for adsorption treatment, wherein the stirring speed is 100r/min, the reaction temperature is 30-50 ℃, and the adsorption time is 20-60 min; wherein the concentration of hexavalent chromium ions in the wastewater is 1-100mg/L, and the addition amount of the modified metallurgical desulfurization slag accounts for 0.2-2g/L of the total amount of the wastewater.
Preferably, the metallurgical desulfurization slag in S1 is from a steel plant or a ferronickel plant.
Preferably, the metallurgical desulfurization slag before treatment in S1 comprises the following components in percentage by mass: SiO 228.8-46.2％， MgO0.2-28％，TFe1.8-6.8％，CaO16.3-87.7％。
Preferably, the metallurgical desulfurization slag treated in the S1 comprises the following components in percentage by mass: SiO 228.9-44.6％， MgO0.3-27％，FeO2.8-7.7％，CaO18.8-86.8％。
Preferably, the adsorption rate of the modified metallurgical desulfurization slag on hexavalent chromium ions in the wastewater reaches 86.7%.
Preferably, the semi-coke doping amount in S2 is 20-30%.
Preferably, the adding amount of the modified metallurgical desulfurization slag in the S3 accounts for 0.8-1g/L of the total amount of the wastewater.
Preferably, the adsorption time in S3 is 50-60 min.
The invention relates to a method for harmlessly treating hexavalent chromium ions by utilizing metallurgical desulfurized slag, which has the working principle that: the invention takes low-cost metallurgical solid waste as raw material, adopts semi coke to modify the metallurgical desulfurization slag, and the modified metallurgical desulfurization slag has porous calcium silicate and calcium aluminum silicate. Meanwhile, the metallurgical desulfurization slag contains certain metal TiO2、MnO、Fe、 FeO、Fe2O3And Fe3O4Containing iron oxide, TiO2MnO, Fe and Fe2+All of them have reducing property, and can reduce Cr (VI) in the solution to Cr (III). The calcium oxide content of the metallurgical desulfurization slag is high, and the solution is alkaline after being dissolved in water, so the reduced Cr (III) is Cr (OH)3Precipitated or otherwise treated with Cr (III)/Fe (III) hydroxide (e.g. Cr)xFe1-xOOH、(CrxFe1-x)(OH)xEtc.) or adsorbed onto the surface of the unreacted material, i.e. the chromium ions are present in a trivalent state without carcinogenic properties and are completely non-carcinogenic.
Has the advantages that: (1) the method adopts the modified metallurgical desulfurization slag to achieve the highest absorption rate of hexavalent chromium ions, which can reach 86.7%; (2) the method not only solves the problem of environmental pollution caused by hexavalent chromium ions, but also greatly improves the comprehensive recovery utilization rate of metallurgical solid waste of iron and steel enterprises, and embodies a new environmental management concept of treating waste with waste; (3) the method is hardly affected by temperature, and good adsorption efficiency can be achieved under the room temperature condition in any season.
Drawings
FIG. 1 is an XRD spectrum of metallurgical desulfurization slag;
FIG. 2 is SEM images of modified metallurgical desulfurization slag obtained under different modification conditions;
FIG. 3 is a relationship between the amount of semi coke added and the adsorption efficiency;
FIG. 4 is a relationship between the amount of adsorbed slag and the adsorption rate according to the present invention;
FIG. 5 is a graph showing the relationship between reaction time and adsorption rate according to the present invention;
FIG. 6 is a graph showing the relationship between the reaction temperature and the adsorption rate according to the present invention.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and substance of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Example 1
The metallurgical desulfurization slag used in this example was the metallurgical desulfurization slag produced by a certain iron and steel enterprise factory in Jiangsu, and the main phase composition of the metallurgical desulfurization slag was analyzed by X-ray diffraction (XRD), as shown in FIG. 1, it was found that the metallurgical desulfurization slag mainly contains CaO and Ca2SiO4And metallic Fe; the components are mainly analyzed by X-ray fluorescence (XRF), and the metallurgical desulfurization slag is mainly composed of CaO and SiO2The compositions of other oxides are shown in tables 1 and 2 below. Crushing the metallurgical desulfurization slag, then carrying out magnetic separation to remove iron, and then carrying out ball milling to obtain powder with a particle size of less than 100 meshes.
TABLE 1 main composition of metallurgical desulfurized slag from iron and steel works
TABLE 2 certain main ingredients of metallurgical desulfurization slag of laterite-nickel ore-nickel iron plant
The desulfurized slag mainly comprises CaO and Ca2SiO4And metallic Fe; total iron TFe (both FeO and Fe) in tables 1 and 22O3And Fe3O4)。
Crushing, magnetic separation and ball milling the metallurgical desulfurization slag, and sieving to obtain the granularity smaller than 100 meshes. Selecting semi-coke as a metallurgical desulfurization slag modifier, mixing the semi-coke with the doping amount (1-40%), stirring for 5-10min, putting the mixture into a wafer-shaped die, pressing the mixture into a wafer-shaped sample with the thickness of about 1.5mm in an oil pressure type powder tablet press under the pressure of 10Mpa, taking out the wafer-shaped sample, putting the wafer-shaped sample into a 105 ℃ oven for 2h, drying, sintering, and selecting the sintering temperature (800-1000 ℃). The obtained modified metallurgical desulfurization slag has loose and porous appearance, and the appearance figure is shown in figure 2.
Example 2
The blue-carbon content of the sample sintered at 800 ℃ is 0.10, 0.20, 0.30 and 0.40g, the sample is respectively 1.00g, the sample is put into a beaker filled with 50mL of simulated hexavalent chromium ion-containing wastewater solution, and the sample is stirred on a constant-temperature magnetic stirrer, the temperature is 30 ℃, and the stirring time is 1 h. Filtering with pinhole filter membrane, collecting supernatant, and testing. The sample treatment at 900 ℃, 1000 ℃ and 1100 ℃ is the same as the above way, and after treatment, 16 groups of liquid to be detected can be obtained in total, and the liquid is placed in a shady and cool place to be stored for subsequent treatment. When the sintering temperature is 1000 ℃ and the adding amount of the semi coke is 0.3g, the adsorption rate reaches 85 percent by utilizing the measurement of an ultraviolet-visible spectrophotometer. The specific relationship is shown in figure 3, the adsorption capacity of the blue carbon doped (4 variables) desulfurization slag is treated at 800 ℃, 900 ℃, 1000 ℃ and 1100 ℃.
Crushing and ball-milling the metallurgical desulfurization slag, and screening the granularity to be less than 100 meshes. 58mL of 0.1mol/L potassium dichromate solution (1/6K) was taken2Cr2O7) Placing the solution into a 1000mL volumetric flask, and adding deionized water to prepare a 100mg/L hexavalent chromium ion standard solution for later use. The hexavalent chromium ion standard solution is diluted to 10mg/L, and 50mL of the hexavalent chromium ion standard solution is measured and placed in a beaker. 1.00g of each of the samples with the blue-carbon content of 0.10, 0.20, 0.30 and 0.40g sintered at the temperature of 800 ℃ is put into a beaker filled with 50mL of simulated chromium-containing wastewater solution and stirred on a constant-temperature magnetic stirrer at the temperature of 30 ℃ for 1 h. Filtering with pinhole filter membrane, collecting supernatant, and testing. The sample treatment at 900 ℃, 1000 ℃ and 1100 ℃ is the same as the above way, and after treatment, 16 groups of liquid to be detected can be obtained in total, and the liquid is placed in a shady and cool place to be stored for subsequent treatment. When the sintering temperature is 1000 ℃ and the adding amount of the semi coke is 0.3g, the adsorption rate reaches 85 percent by utilizing the measurement of an ultraviolet-visible spectrophotometer. The specific relationship is shown in FIG. 3, and the adsorption capacity of the desulfurization residue is different at different treatment temperatures (4 temperatures) for samples containing 0.10 g of semi coke, 0.20 g of semi coke, 0.30 g of semi coke and 0.40g of semi coke.
Example 3
58mL of 0.1mol/L potassium dichromate solution (1/6K) was taken2Cr2O7) Placing the solution into a 1000mL volumetric flask, and adding deionized water to prepare a 100mg/L hexavalent chromium ion standard solution for later use. The hexavalent chromium ion standard solution is diluted to 10mg/L, and 50mL of the hexavalent chromium ion standard solution is measured and placed in a beaker. 0.4g of modified metallurgical desulfurization slag is weighed and poured into a beaker, a stirrer is added, and the mixture is stirred on a constant-temperature magnetic stirrer at the temperature of 30 ℃ for 1 hour. Filtering with pinhole filter membrane, taking outAnd (5) supernatant fluid to be tested. The adsorption rate is up to 84.2% by using ultraviolet-visible spectrophotometer. In addition, when other experimental conditions are unchanged, 0.2g of modified metallurgical desulfurization slag is weighed, and the measured adsorption rate is 77.6%; when 0.4g of the modified metallurgical desulfurization slag is weighed, the measured adsorption rate is 81.1; when 0.6g of modified metallurgical desulfurization slag is weighed, the measured adsorption rate is 84.2%; when 0.8g of the modified metallurgical desulfurization slag is weighed, the measured adsorption rate is 85 percent; (see FIG. 4 for details)
Example 4
58mL of 0.1mol/L potassium dichromate solution (1/6K) was taken2Cr2O7) Placing the solution into a 1000mL volumetric flask, and adding deionized water to prepare a 100mg/L hexavalent chromium ion standard solution for later use. The hexavalent chromium ion standard solution is diluted to 10mg/L, and 50mL of the hexavalent chromium ion standard solution is measured and placed in a beaker. Weighing 1g of modified metallurgical desulfurization slag, pouring the weighed modified metallurgical desulfurization slag into a beaker, adding a stirrer, and stirring the mixture on a constant-temperature magnetic stirrer at the temperature of 30 ℃ for 30 min. Filtering with pinhole filter membrane, collecting supernatant, and testing. The adsorption rate is up to 63.3% by using ultraviolet-visible spectrophotometer. In addition, when other experimental conditions are unchanged and the stirring time is 20min, the measured adsorption rate is 49.5%; when the stirring time is 40min, the measured adsorption rate is 71.8%; when the stirring time was 50min, the adsorption rate was measured to be 84.5%. When the stirring time was 1 hour, the adsorption rate was found to be 85.4%. (see FIG. 5 for details)
Example 5
58mL of 0.1mol/L potassium dichromate solution (1/6K) was taken2Cr2O7) Placing the mixture into a 1000mL volumetric flask, adding deionized water to prepare 100mg/L Cr6+Standard solution, ready for use. Dilute Cr6+The standard solution was adjusted to 10mg/L and 50mL was measured and placed in a beaker. Weighing 1g of modified metallurgical desulfurization slag, pouring the weighed modified metallurgical desulfurization slag into a beaker, adding a stirrer, and stirring the mixture on a constant-temperature magnetic stirrer at the temperature of 35 ℃ for 1 hour. Filtering with pinhole filter membrane, collecting supernatant, and testing. The adsorption rate is up to 86.2% by using ultraviolet-visible spectrophotometer. In addition, when other experimental conditions are unchanged and the temperature is 30 ℃, the adsorption rate is 85.4 percent; when the temperature is 40 ℃, the adsorption rate is 84.5 percent; when the temperature is 4The adsorption rate obtained at 5 ℃ is 84%; when the temperature was 50 ℃, the adsorption rate was 83.7% (see fig. 6 for a specific relationship).
Claims (8)
1. The method for harmlessly treating hexavalent chromium ions by utilizing metallurgical desulfurization slag is characterized by comprising the following steps of:
s1, crushing the metallurgical desulfurization slag, carrying out reverse magnetic separation, ball milling and screening until the granularity is less than 100 meshes, and obtaining fine powder of the metallurgical desulfurization slag after iron removal;
s2, selecting semi-coke as a metallurgical desulfurization slag modifier, mixing the semi-coke with the doping amount of 1-40%, tabletting and re-sintering, wherein the sintering temperature is 800-1000 ℃;
s3, putting the metallurgical desulfurization slag modified by the S2 into wastewater containing hexavalent chromium ions for adsorption treatment, wherein the stirring speed is 100r/min, the reaction temperature is 30-50 ℃, and the adsorption time is 20-60 min; wherein the concentration of hexavalent chromium ions in the wastewater is 1-100mg/L, and the addition amount of the modified metallurgical desulfurization slag accounts for 0.2-2g/L of the total amount of the wastewater.
2. The method for harmlessly treating hexavalent chromium ions by using the metallurgical desulfurization slag according to claim 1, wherein the metallurgical desulfurization slag in S1 is from a steel plant or a ferronickel plant.
3. The method for harmlessly treating hexavalent chromium ions by using the metallurgical desulfurization slag according to claim 1 or 2, wherein the metallurgical desulfurization slag before treatment in S1 comprises, by mass percent: SiO 228.8-46.2％，MgO0.2-28％，TFe1.8-6.8％，CaO16.3-87.7％。
4. The method for harmlessly treating hexavalent chromium ions by using the metallurgical desulfurization slag according to claim 1 or 2, wherein the metallurgical desulfurization slag treated in the S1 comprises, by mass percent: SiO 228.9-44.6％，MgO0.3-27％，FeO2.8-7.7％，CaO18.8-86.8％。
5. The method for harmlessly treating hexavalent chromium ions by using the metallurgical desulfurization slag according to claim 1, wherein the adsorption rate of the modified metallurgical desulfurization slag on hexavalent chromium ions in wastewater reaches 86.7%.
6. The method for harmlessly treating hexavalent chromium ions by using metallurgical desulfurization slag according to claim 1, wherein the amount of semi coke added in S2 is 20% -30%.
7. The method for harmlessly treating hexavalent chromium ions by using metallurgical desulfurization slag according to claim 1, wherein the modified metallurgical desulfurization slag is added in an amount of 0.8 to 1g/L based on the total amount of wastewater in S3.
8. The method for harmlessly treating hexavalent chromium ions by using metallurgical desulfurization slag according to claim 1, wherein the adsorption time in S3 is 50-60 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114058861A (en) * | 2021-11-27 | 2022-02-18 | 王强 | Method for harmlessly treating chromium slag by using injection desulfurization process |
| WO2022257352A1 (en) * | 2021-06-07 | 2022-12-15 | 江苏科技大学 | Method for harmlessly treating hexavalent chromium ions by using metallurgical desulfurization slag |
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| CN103480635A (en) * | 2013-09-26 | 2014-01-01 | 李平 | Method for comprehensively treating waste iron oxide desulfurizer and chromium slag |
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| CN111250034A (en) * | 2020-03-24 | 2020-06-09 | 江苏科技大学 | Modification method and application of desulfurization slag |
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| CN102698707A (en) * | 2012-06-29 | 2012-10-03 | 武汉钢铁(集团)公司 | Industrial wastewater adsorbent and preparation method thereof |
| CN105854784A (en) * | 2015-01-19 | 2016-08-17 | 中国科学院过程工程研究所 | Method for preparing environmental protection material used for sewage treatment by reforming metallurgical dregs |
| CN113461097B (en) * | 2021-06-07 | 2022-08-19 | 江苏科技大学 | Method for harmlessly treating hexavalent chromium ions by utilizing metallurgical desulfurization slag |
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| CN103480635A (en) * | 2013-09-26 | 2014-01-01 | 李平 | Method for comprehensively treating waste iron oxide desulfurizer and chromium slag |
| CN106179247A (en) * | 2016-08-08 | 2016-12-07 | 东北农业大学 | A kind of Cr VI adsorbent and its preparation method and application |
| CN106865729A (en) * | 2017-03-22 | 2017-06-20 | 中钢集团武汉安全环保研究院有限公司 | A kind of method of utilization molten iron pretreatment desulfurizing Slag treatment containing chromium heavy metal wastewater thereby |
| CN111250034A (en) * | 2020-03-24 | 2020-06-09 | 江苏科技大学 | Modification method and application of desulfurization slag |
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| WO2022257352A1 (en) * | 2021-06-07 | 2022-12-15 | 江苏科技大学 | Method for harmlessly treating hexavalent chromium ions by using metallurgical desulfurization slag |
| CN114058861A (en) * | 2021-11-27 | 2022-02-18 | 王强 | Method for harmlessly treating chromium slag by using injection desulfurization process |
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