CN112239259A - Chemical remover for heavy metal polluted wastewater treatment and preparation method and application thereof - Google Patents
Chemical remover for heavy metal polluted wastewater treatment and preparation method and application thereof Download PDFInfo
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- CN112239259A CN112239259A CN202010856367.9A CN202010856367A CN112239259A CN 112239259 A CN112239259 A CN 112239259A CN 202010856367 A CN202010856367 A CN 202010856367A CN 112239259 A CN112239259 A CN 112239259A
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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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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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
- 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 chemical remover for treating heavy metal polluted wastewater, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing biomass powder with a solution containing an M source, adding a complexing agent solution under stirring to obtain a mixture, reacting, drying, and roasting to obtain the chemical remover, wherein the M source is selected from a manganese source and/or an iron source. According to the chemical remover prepared by the invention, the prepared chemical remover is added into the waste water polluted by lead, cadmium and arsenic according to a certain mass ratio, the removal rates of effective cadmium and lead are respectively more than 95% and 90%, and the removal rate of arsenic is more than 80%. The chemical remover fully utilizes agricultural solid wastes, and has simple preparation process and low cost; and the prepared remover has good effect of removing heavy metals, and can be used for treating wastewater polluted by lead, cadmium and arsenic.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a chemical remover for treating heavy metal polluted wastewater, a preparation method thereof, and application thereof in heavy metal polluted wastewater treatment.
Background
Fresh water is an important resource for natural environment and agricultural production on which humans rely for survival. However, environmental pollution and ecological damage are increasingly severe, which seriously affect human health and survival, and among them, heavy metal elements have serious pollution and damage to the environment, and the treatment of multi-metal wastewater has become the focus of current environmental science research.
At present, the heavy metal sewage treatment mainly comprises several types of methods such as a physical chemical method, a biological method and the like. The physical and chemical method is to separate and remove heavy metal ions by using physical properties or physical and chemical properties of substances, and mainly comprises ion exchange, adsorption, solvent extraction, air flotation, membrane separation and the like. The method generally consumes a large amount of capital, manpower and material resources, and is suitable for treating sewage with higher requirements on the quality of the effluent. The biological method mainly comprises the steps of planting heavy metal tolerant plants and heavy metal super-enriched plants. The heavy metals in the water can be enriched in the harvestable parts of the plant roots and the overground branches of the plants by the plants through the modes of absorption, precipitation or enrichment and the like, and the heavy metal concentration in the wastewater or the water body can be reduced by harvesting or removing the branches of the plants enriched with the heavy metals, so that the pollution is treated, and the environment is treated. However, hyper-enriched plants are characterized by slow growth, low biomass, special growing environment, etc., are difficult to meet economic and environmental requirements, and are often limited by local climatic conditions and available plant species. The chemical method has the advantages of wide application range, large processing capacity, multiple method means, quick response, obvious effect and the like, so the chemical method has better application prospect. The chemical method is a method of purifying water by adding a proper chemical agent and converting heavy metal ions into insoluble metal compounds by utilizing the chemical reaction between the heavy metal ions and the chemical agent or converting the heavy metal ions into non-toxic or low-toxic substances by the chemical reaction. The chemical agents commonly used at present have the following problems: (1) the usage amount is large, and the generated sludge amount is large; (2) heavy metal ions with different properties in the sewage cannot be removed simultaneously; arsenic, cadmium and lead ions coexist in polluted water under acidic conditions, but because of different properties and adsorption competition relationship among the arsenic, cadmium and lead ions, no single remover can remove the arsenic, cadmium and lead ions at the same time so far, and 3) part of precipitants are remained in water, so that secondary pollution is easily caused. Therefore, the preparation of the environment-friendly heavy metal remover with good removal effect becomes a key technical problem in the treatment of heavy metal polluted wastewater in China.
Disclosure of Invention
In view of the defects of the prior art, the first object of the invention is to provide a preparation method of a chemical remover for treating heavy metal polluted wastewater.
The second purpose of the invention is to provide the remover for treating the heavy metal polluted wastewater, which is prepared by the preparation method.
The third purpose of the invention is to provide the application of the remover for treating the heavy metal polluted wastewater, which is prepared by the preparation method, in the treatment of the heavy metal polluted wastewater.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention relates to a preparation method of a chemical remover for treating heavy metal polluted wastewater, which comprises the following steps:
mixing biomass powder with a solution containing an M source, adding a complexing agent solution under stirring to obtain a mixture, reacting, drying, and roasting to obtain the chemical remover, wherein the M source is selected from a manganese source and/or an iron source.
Preferably, the biomass in the biomass powder is rice straw powder and/or wheat straw.
Preferably, the biomass powder is obtained by the following method: the rice straw is cleaned by ultrasonic, dried and crushed, and then screened by a 40-mesh screen, and undersize products are taken.
Further preferably, the time for ultrasonically cleaning the rice straw is 10min or more.
In a preferred embodiment, the concentration of M element in the solution containing M source is 0.01-0.1mol/L, preferably 0.05-0.1 mol/L.
Preferably, the M source is selected from a manganese source and an iron source, and the molar ratio of manganese element: iron element 1: 0.5 to 1.
The complexing agent is added in the invention, so that the metal elements can be uniformly distributed in the chemical remover, and the chemical remover obtained after roasting can simultaneously realize the high-efficiency absorption and removal of arsenic, cadmium and lead ions.
Preferably, the manganese source is selected from at least one of manganese nitrate, manganese nitrate tetrahydrate and manganese nitrate hexahydrate.
In a preferred embodiment, the iron source is at least one selected from iron nitrate and iron nitrate nonahydrate
Preferably, the addition amount of the M source is 0.5-2% of the mass of the straw powder.
Preferably, the complexing agent in the complexing agent solution is at least one selected from citric acid and oxalic acid.
In a preferable scheme, the concentration of the complexing agent in the complexing agent solution is 0.01-0.1mol/L, and preferably 0.05-0.1 mol/L.
In a preferred embodiment, the complexing agent: and M is 1: 1-0.5.
In a preferable scheme, the reaction is carried out under stirring, the stirring speed is 150-300 rpm, the reaction temperature is room temperature, and the reaction time is 60-120 min. The reaction of the invention can be carried out fully at room temperature, and the preparation cost is greatly reduced.
In a preferable scheme, the drying temperature is 105-120 ℃, and the drying time is 24-36 h.
In the preferable scheme, the roasting is carried out in a protective atmosphere, the roasting temperature is 550-700 ℃, the roasting time is 150-180 min, and the heating rate is 5-7 ℃/min.
In the actual operation process, the roasted product is cooled, ground and sieved by a 40-mesh sieve, and the sieve is taken down to obtain the chemical remover.
The invention also provides the chemical remover prepared by the preparation method.
The invention also provides application of the chemical remover prepared by the preparation method, and the chemical remover is used for treating heavy metal polluted wastewater.
The application method comprises the following steps: adding the chemical remover into the heavy metal polluted wastewater, stirring until the mixture is uniform, wherein the treatment time is at least 24h, and the heavy metal polluted wastewater is obtained by the following steps: chemical remover 1000: (1-5),
the heavy metal ions in the heavy metal polluted wastewater contain Cd2+、Pb2+、AsO4 3-、HAsO4 2-、H2AsO4 1-、H3AsO4、H1AsO3 2-、H2AsO3 1-、H3AsO3At least one of them.
The inventor surprisingly finds that the chemical remover prepared by the invention can simultaneously remove arsenic, cadmium and lead ions in water, and in the water containing arsenic, cadmium and lead ions, the chemical remover can realize high-efficiency removal only by adding the chemical remover.
The invention has the following advantages:
1. the heavy metal remover disclosed by the invention is rich in Lewis acidic sites, hydroxyl functional groups and heavy metal cations (Cd)2+、Pb2+) And the like, through surface adsorption and coordination, heavy metal precipitates are formed under the alkalescent condition, so that the removal effect of the heavy metals is enhanced, and the chemical remover has the more unexpected effects that the chemical remover can simultaneously remove arsenic, cadmium and lead ions in water,
3. the main raw materials of the invention are rice straws which are all agricultural wastes, the raw materials have wide sources and low cost, and a new way is provided for the resource utilization of the agricultural wastes.
4. The main raw materials of the heavy metal remover comprise rice straws, citric acid or oxalic acid, manganese nitrate and ferric nitrate, and the prepared heavy metal remover comprises carbon, iron and manganese as main elements and is an environment-friendly heavy metal remover.
Drawings
FIG. 1 is a scanning electron micrograph of a chemical remover obtained in example 1 of the present invention;
FIG. 2 is an EDX diagram of the chemistry obtained in example 1 of the present invention;
FIG. 3 is a diagram showing the effect of the chemical remover prepared in example 1 on removing Cd, Pb and As from wastewater containing Pb, Cd and As complex pollutants;
FIG. 4 is a diagram showing the effect of the chemical remover prepared in example 2 on removing Cd, Pb and As from the lead-cadmium combined polluted wastewater.
FIG. 5 is a diagram showing the effect of the chemical remover prepared in example 3 on removing Cd, Pb and As from wastewater containing Pb, Cd and As complex pollutants;
FIG. 6 is a diagram showing the effect of the chemical remover prepared in example 4 on removing Cd, Pb, and As from the Pb-Cd composite polluted wastewater.
FIG. 7 is a diagram showing the effect of the chemical remover prepared in comparative example 1 on removing Cd, Pb and As in the lead-cadmium combined polluted wastewater.
Detailed Description
The following examples are intended to further illustrate the invention without limiting it.
Example 1
Cleaning 10g of rice straw in an ultrasonic cleaning instrument for 10min, drying, crushing, and sieving with a 40-mesh sieve for later use; 0.1 mol. L of the preparation-1Citric acid and Mn (NO)3)2Solution, 18ml of Mn (NO)3)2Slowly adding the solution into 10g of rice straw, slowly adding 18ml of citric acid solution and 40ml of ultrapure water along the inner wall of the container, and continuously stirring and mixing; continuously stirring the mixed solution for 120min at the speed of 300rpm under the action of a magnetic stirrer, taking out the stirrer, and drying in a drying oven at the constant temperature of 105 ℃ to constant weight; placing the dried material in a sealed container, heating to 550 deg.C at a heating rate of 5 deg.C/min in a muffle furnace, continuously calcining for 180min, coolingGrinding and sieving with a 40-mesh sieve to prepare the wastewater heavy metal remover.
100ml of lead-cadmium-arsenic polluted wastewater is measured, 0.5g of the remover is added, and the mixture is uniformly mixed. Sampling at 60min, 120min, 240min, 480min, 720min and 24h respectively, determining the content of Cd, Pb and As in the wastewater, and detecting that the removal rate of Pb in the wastewater after 24h is 99%, the removal rate of Cd is 95% and the removal rate of As is 85%.
Example 2
Cleaning 10g of rice straw in an ultrasonic cleaning instrument for 10min, drying, crushing, and screening with a 40-mesh screen for later use; 0.05 mol. L of the preparation-1Oxalic acid and Fe (NO)3)2Solution, 18ml of Fe (NO)3)2Slowly adding the solution into 10g of rice straws, slowly adding 18ml of oxalic acid solution and 40ml of ultrapure water along the inner wall of the container, and continuously stirring and mixing; continuously stirring the mixed solution for 120min at the speed of 300rpm under the action of a magnetic stirrer, taking out the stirrer, and drying in a drying oven at the constant temperature of 105 ℃ to constant weight; and (3) placing the dried substance in a sealed container, heating to 550 ℃ at the heating rate of 5 ℃/min in a muffle furnace, continuously roasting for 180min, cooling, grinding and sieving with a 40-mesh sieve after roasting is finished, and preparing the wastewater heavy metal remover.
100ml of lead-cadmium-arsenic polluted wastewater is measured, 0.4g of the remover is added, and the mixture is uniformly mixed. Sampling at 60min, 120min, 240min, 480min, 720min and 24h respectively, determining the content of Cd, Pb and As in the wastewater, and detecting that the removal rate of Pb in the wastewater after 24h is 99%, the removal rate of Cd is 80% and the removal rate of As is 75%.
Example 3
Cleaning 10g of rice straw in an ultrasonic cleaning instrument for 10min, drying, crushing, and sieving with a 40-mesh sieve for later use; 0.1 mol. L of the preparation-1Citric acid, Mn (NO)3)2Solution and Fe (NO)3)2Solution 9ml of Mn (NO)3)2The solution was mixed with 9ml of Fe (NO)3)2Slowly adding the solution into 10g of rice straw, slowly adding 18ml of citric acid solution and 40ml of ultrapure water along the inner wall of the container, and continuously stirring and mixing; the mixed solution was continuously stirred at 300rpm under the action of a magnetic stirrer 120min, taking out the stirrer, and drying in a drying oven at 105 deg.C to constant weight; and (3) placing the dried substance in a sealed container, heating to 550 ℃ at the heating rate of 5 ℃/min in a muffle furnace, continuously roasting for 180min, cooling, grinding and sieving with a 40-mesh sieve after roasting is finished, and preparing the wastewater heavy metal remover.
100ml of lead-cadmium-arsenic polluted wastewater is measured, 0.5g of the remover is added, and the mixture is uniformly mixed. Sampling at 60min, 120min, 240min, 480min, 720min and 24h respectively, determining the content of Cd, Pb and As in the wastewater, and detecting that the removal rate of Pb in the wastewater after 24h is 99%, the removal rate of Cd is 90% and the removal rate of As is 84%.
Example 4
Cleaning 10g of rice straw in an ultrasonic cleaning instrument for 10min, drying, crushing, and screening with a 40-mesh screen for later use; 0.01 mol. L of the preparation-1Oxalic acid and Fe (NO)3)2Solution, 18ml of Fe (NO)3)2Slowly adding the solution into 10g of rice straws, slowly adding 18ml of oxalic acid solution and 40ml of ultrapure water along the inner wall of the container, and continuously stirring and mixing; continuously stirring the mixed solution for 120min at the speed of 300rpm under the action of a magnetic stirrer, taking out the stirrer, and drying in a drying oven at the constant temperature of 105 ℃ to constant weight; and (3) placing the dried substance in a sealed container, heating to 550 ℃ at the heating rate of 5 ℃/min in a muffle furnace, continuously roasting for 180min, cooling, grinding and sieving with a 40-mesh sieve after roasting is finished, and preparing the wastewater heavy metal remover.
100ml of lead-cadmium-arsenic polluted wastewater is measured, 0.4g of the remover is added, and the mixture is uniformly mixed. Sampling at 60min, 120min, 240min, 480min, 720min and 24h respectively, determining the content of Cd, Pb and As in the wastewater, and detecting that the removal rate of Pb in the wastewater after 24h is 90%, the removal rate of Cd is 70% and the removal rate of As is 75%.
Comparative example 1
Cleaning 10g of rice straw in an ultrasonic cleaning instrument for 10min, drying, crushing, and screening with a 40-mesh screen for later use; 0.01 mol. L of the preparation-1Fe(NO3)2Solution, 18ml of Fe (NO)3)2Slowly adding the solution and 40ml of ultrapure water into 10g of rice straws; stirring the mixed solution under magnetic forceContinuously stirring at 300rpm for 120min under the action of the stirrer, taking out the stirrer, and drying in a drying oven at 105 ℃ to constant weight; and (3) placing the dried substance in a sealed container, heating to 550 ℃ at the heating rate of 5 ℃/min in a muffle furnace, continuously roasting for 180min, cooling, grinding and sieving with a 40-mesh sieve after roasting is finished, and preparing the wastewater heavy metal remover.
100ml of lead-cadmium-arsenic polluted wastewater is measured, 0.4g of the remover is added, and the mixture is uniformly mixed. Sampling at 60min, 120min, 240min, 480min, 720min and 24h respectively, determining the content of Cd, Pb and As in the wastewater, and detecting that the removal rate of Pb, the removal rate of Cd and the removal rate of As in the wastewater is 70%, 60% and 55% after 24 h.
Comparative example 2
According to the iron oxide-loaded composite biochar material prepared according to the patent application No. CN201510037103.X, the same application method As that of the embodiment 3 is adopted, the removal rate of Pb in the wastewater after 24 hours is 63%, the removal rate of Cd is 41%, and the removal rate of As is 25%.
Claims (10)
1. A preparation method of a chemical remover for treating heavy metal polluted wastewater is characterized by comprising the following steps: the method comprises the following steps:
mixing biomass powder with a solution containing an M source, adding a complexing agent solution under stirring to obtain a mixture, reacting, drying, and roasting to obtain the chemical remover, wherein the M source is selected from a manganese source and/or an iron source.
2. The method for preparing the chemical remover for heavy metal polluted wastewater treatment according to claim 1, wherein the chemical remover comprises: the biomass in the biomass powder is rice straw and/or wheat straw; the biomass powder is obtained by the following steps: ultrasonically cleaning rice straw, drying, crushing, sieving with a 40-mesh sieve, taking undersize, and ultrasonically cleaning the rice straw for over 10 min.
3. The method for preparing the chemical remover for heavy metal polluted wastewater treatment according to claim 1, wherein the chemical remover comprises:
the manganese source is selected from at least one of manganese nitrate, manganese nitrate tetrahydrate and manganese nitrate hexahydrate;
the iron source is at least one of ferric nitrate and ferric nitrate nonahydrate.
4. The method for preparing the chemical remover for heavy metal polluted wastewater treatment according to claim 1, wherein the chemical remover comprises: in the solution containing the M source, the concentration of the M element is 0.01-0.1 mol/L;
the addition amount of the M source is 0.5-2% of the mass of the straw powder.
5. The method for preparing a chemical remover for heavy metal contaminated wastewater treatment according to claim 1 or 4, wherein:
the M source is selected from a manganese source and an iron source, and the molar ratio of manganese element: iron element 1: 0.5 to 1.
6. The method for preparing the chemical remover for heavy metal polluted wastewater treatment according to claim 1, wherein the chemical remover comprises: the complexing agent in the complexing agent solution is at least one selected from citric acid and oxalic acid;
in the complexing agent solution, the concentration of the complexing agent is 0.01-0.1 mol/L.
7. The method for preparing the chemical remover for heavy metal polluted wastewater treatment according to claim 1, wherein the chemical remover comprises: in the mixture, the complexing agent: and M is 1: 1-0.5.
8. The method for preparing the chemical remover for heavy metal polluted wastewater treatment according to claim 1, wherein the chemical remover comprises: the roasting is carried out in a protective atmosphere, the roasting temperature is 550-700 ℃, the roasting time is 150-180 min, and the heating rate is 5-7 ℃/min.
9. The chemical remover prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the chemical remover prepared by the preparation method according to any one of claims 1 to 8, wherein: the chemical remover is used for treating heavy metal polluted wastewater.
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| CN114345372A (en) * | 2021-12-14 | 2022-04-15 | 广东环境保护工程职业学院 | Sulfur-containing compound and preparation method and application thereof |
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