CN112375571A - Molybdenum-polluted soil repairing agent and repairing method - Google Patents
Molybdenum-polluted soil repairing agent and repairing method Download PDFInfo
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Abstract
The invention discloses a molybdenum contaminated soil repairing agent and a repairing method, wherein the repairing agent comprises the following components: hematite, ferric sulphate and ammonium sulphate; the repairing method comprises the following steps: analyzing the biological available molybdenum and pH in the molybdenum-polluted soil; adding a preset molybdenum-polluted soil remediation agent into molybdenum-polluted soil based on the analysis result; stirring uniformly, moistening soil, and maintaining for 7-30 days. The ferric sulfate and the ammonium sulfate in the repairing agent can reduce the pH value of the soil after being hydrolyzed, so that MoO in the soil can be reduced4 2‑Is adsorbed and fixed by soil; meanwhile, the hydrolysate of hematite and ferric sulfate can be mixed with MoO4 2‑Form ferromolybdenum salt precipitate to fix molybdenum in soil and reduce the mobility of molybdenum in soil. The raw materials used in the repairing agent are cheap and easy to obtain, the operation is simple, the adaptability is strong, and the popularization is easy; at the same time, the addition of the repairing agent is notAffecting the continuous use of the farmland.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a molybdenum-polluted soil remediation agent and a remediation method.
Background
Molybdenum is a trace element necessary for human bodies, animals and plants, and the deficiency or excess of molybdenum can cause great harm to the life health of human bodies, and can cause the obstruction of the energy metabolism process in vivo, the lack of oxygen of cardiac muscles and the focal necrosis of cardiac muscles, the easy occurrence of kidney stones and urethral stones, the increase of the illness probability of iron-deficiency anemia and the initiation of dental caries.
Molybdenum reserves are in the forefront of the world in China, and molybdenum alloy have wide application in a plurality of important fields of steel industry, agriculture, chemical industry, oil exploitation, environmental protection and the like, and become an important raw material in national economy. With the rapid development of molybdenum mining, smelting and processing industries, molybdenum pollution is also generated. In recent years, molybdenum pollution of farmland occurs to different degrees in many areas of China, for example, the content of molybdenum in farmland soil around a certain molybdenum ore area in east Fujian reaches 325.6 mg.kg-1Over 87 times the background value of molybdenum in the soil of the area; the molybdenum in the farmland surrounding the molybdenum ore area of the cucurbit island seriously exceeds the standard. The excessive molybdenum in the farmland seriously affects the food safety, and the problem of farmland molybdenum pollution is solved.
The farmland molybdenum contaminated soil remediation technology mainly comprises two types: one is a technique for reducing the molybdenum content in soil, such as chemical leaching, plant extraction, electrokinetic remediation, and the like; the other is a repair technique for stabilizing the molybdenum in the soil and reducing the mobility of the molybdenum, such as chemical passivation and the like. At present, researchers have low attention on molybdenum-polluted soil remediation, and in the prior art, a molybdenum-polluted soil leaching remediation method (CN110586641A), a method for remedying heavy metal-polluted soil by using macleaya cordata and application thereof (CN104249077A) respectively carry out chemical leaching and plant extraction to remediate molybdenum-polluted soil, so that the chemical leaching is high in cost and easy to cause secondary pollution; the plant extraction and repair efficiency is low and the time is long.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a molybdenum-polluted soil repairing agent and a repairing method.
The invention discloses a molybdenum-polluted soil remediation agent, which comprises the following components in part by weight: hematite, iron sulphate and ammonium sulphate.
As a further improvement of the invention, the hematite is 15-40 parts by weight, the ferric sulfate is 10-30 parts by weight, and the ammonium sulfate is 50-80 parts by weight.
As a further improvement of the invention, the weight ratio of the hematite to the ferric sulfate to the ammonium sulfate is 1:1: 3.
As a further improvement of the invention, the hematite is Fe2O3The content of the active ingredients is more than 65 percent, and the screening rate of the active ingredients after being screened by a dry screen with 20 meshes is more than 90 percent.
As a further improvement of the invention, the molybdenum-polluted soil remediation agent is suitable for remediation of molybdenum-polluted soil with the pH of 3-12.
As a further improvement of the invention, the molybdenum-polluted soil remediation agent is suitable for remediation of molybdenum-polluted soil with the pH of 6-9.
The invention also discloses a method for restoring the molybdenum-polluted soil, which comprises the following steps:
analyzing the biological available molybdenum and pH in the molybdenum-polluted soil;
adding a preset molybdenum-polluted soil remediation agent into the molybdenum-polluted soil based on the analysis result;
stirring uniformly, moistening soil, and maintaining for 7-30 days.
As a further improvement of the invention, the addition amount of the molybdenum-polluted soil remediation agent is 10-40% of the mass of the molybdenum-polluted soil.
As a further improvement of the invention, before maintenance, the soil is wetted until the water content of the soil is 20-60%.
As a further improvement of the method, after the remediation, the pH of the molybdenum-polluted soil is between 5.5 and 6.5.
Compared with the prior art, the invention has the beneficial effects that:
the ferric sulfate and the ammonium sulfate in the repairing agent can reduce the pH value of the soil after being hydrolyzed, so that MoO in the soil can be reduced4 2-Is adsorbed and fixed by soil; meanwhile, the hydrolysate of hematite and ferric sulfate can be mixed with MoO4 2-Form ferromolybdenum salt precipitate to fix molybdenum in soil and reduce the mobility of molybdenum in soil. The raw materials used in the repairing agent of the invention are cheap and easy to useThe preparation method is simple to operate, strong in adaptability and easy to popularize; meanwhile, the addition of the repairing agent does not influence the continuous use of the farmland.
Drawings
Fig. 1 is a flowchart of a method for remediating molybdenum-contaminated soil according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention; meanwhile, those whose specific conditions are not specified in the following examples are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention is described in further detail below with reference to the attached drawing figures:
the technology is different from technologies for reducing the molybdenum content in soil such as chemical leaching, plant extraction and electric restoration, and the restoration technology mainly based on chemical passivation for stabilizing the molybdenum in the soil and reducing the mobility of the molybdenum in the soil has the advantages of simple operation, low cost, quick response and the like. At present, no report of restoring farmland molybdenum-polluted soil by using a chemical passivation method exists, so that research and application values of farmland molybdenum-polluted passivation research are realized.
Research and analysis show that the molybdenum entering the soil has two main forms: the molybdenum in the particle state is easily oxidized into molybdate radicals with high mobility under alkaline or oxidation conditions, and the molybdate radicals are reduced and fixed again in an acidic environment; and the ionic molybdenum is easily adsorbed by iron, manganese oxides, clay minerals and the like, so that the effectiveness of the molybdenum in the soil is reduced. The form of molybdenum present in soil is closely related to the pH of the soil. When the pH is less than 2.5, MoO4 2-Conversion to MoO2 2+(ii) a When the pH value is more than 4, the molybdenum in the soil is MoO4 2-The form exists; when the pH value is 3-5, the molybdenum can be completely adsorbed; the pH value is more than 8, and the molybdenum can hardly be adsorbed and has strong mobility. In order to reduce the harm of molybdenum in the soil, on one hand, an adsorbent can be added to increase the adsorption of ionic molybdenum in the soil; on the other hand, the pH value of the soil is reduced, so that the granular molybdenum is reduced and fixed, and the content of the effective molybdenum in the soil is reduced.
Hematite is iron oxide and has better adsorbability to ionic molybdenum, so as to form ferromolybdenum coprecipitate; ferric sulfate it forms a series of positively charged hydrolysates with water molecules, e.g. Fe (OH)2+、Fe(OH)2 +、Fe2(OH)2 4+、Fe4(OH)6 6+And the hydrolysate can interact with the molybdate radical with negative charge in the modes of electrostatic adsorption, surface complexation, coprecipitation and the like, so that the reduction of molybdate radical ions is promoted. The ammonium sulfate can acidify the soil, reduce the mobility of molybdenum, fix the molybdenum by the soil and the repairing agent and increase the nitrogen source in the soil.
In view of the above, the present invention provides a molybdenum-contaminated soil remediation agent, comprising: hematite, iron sulphate and ammonium sulphate.
Further, the addition amount of the components is as follows according to the parts by weight: 15-40 parts of hematite, 10-30 parts of ferric sulfate and 50-80 parts of ammonium sulfate. Preferably, the hematite is 15-20 parts, the ferric sulfate is 20-30 parts, and the ammonium sulfate is 60-80 parts. More preferably, the weight ratio of hematite to ferric sulphate to ammonium sulphate is 1:1: 3. Wherein, the selection of the weight ratio of the components is based on the influence on the reduction range of the pH value of the soil, the reduction range of the pH value of the soil is probably small, and the reduction of the effective molybdenum is not ideal; the pH value of the soil is greatly reduced, the soil acidity is low, and the continuous use of the soil is influenced; when the weight ratio of hematite to ferric sulfate to ammonium sulfate is 1:1:3, the pH value of the soil is reduced to a proper value, a large amount of molybdenum is fixed by the soil, the content of effective molybdenum is greatly reduced, and meanwhile, the hydrolysis products of hematite and ferric sulfate and MoO4 2-The ferromolybdenum salt formed in the environment is most precipitated and stable。
Further, the hematite of the present invention contains Fe2O3The content of the active ingredients is more than 65 percent, and the sieving rate of the active ingredients after dry sieving with 20 meshes is more than 90 percent; wherein, the content of Fe is low2O3The hematite has more impurities and lower activity, and cannot achieve the rational repair effect.
Further, the molybdenum-polluted soil remediation agent is suitable for remediation of molybdenum-polluted soil with the pH of 3-12; the method is most suitable for restoring the molybdenum polluted soil with the pH value of 6-9. After the remediation, the pH value of the molybdenum-polluted soil is between 5.5 and 6.5.
As shown in fig. 1, the present invention provides a method for repairing molybdenum-contaminated soil, comprising:
step 1, analyzing the biological available molybdenum and pH in the molybdenum-polluted soil;
step 2, adding a preset molybdenum-polluted soil remediation agent into molybdenum-polluted soil based on an analysis result; wherein the content of the first and second substances,
the addition amount of the molybdenum-polluted soil remediation agent is 10-40% of the mass of the molybdenum-polluted soil, and the addition amount is closely related to the pH value of the polluted soil; for example, the addition amount is such that the addition amount of the remediation agent is 10% per soil pH reduction, for example, the soil pH is 8, the remediation agent is 10% per soil pH reduction, the soil pH is reduced to about 7, the addition amount is 20%, and the soil pH is reduced to about 6.
Step 3, uniformly stirring, adding a certain amount of water into the matrix to keep the soil moist, and maintaining; wherein the content of the first and second substances,
in the step, the soil is wetted until the water content of the soil is 20% -60%, and preferably wetted until the water content of the soil is 25% -40%;
the curing time in the step is 7-30 days, and preferably 21-30 days.
After the remediation is carried out in the steps 1-3, the pH value of the molybdenum-polluted soil is 5.5-6.5.
Example 1
Weighing 150g of hematite in a beaker for later use, and recording as a repairing agent A; weighing 150g of ferric sulfate in a beaker for later use, and recording as a repairing agent B; weighing 150g of ammonium sulfate in a beaker for later use, and recording as a repairing agent C; 30g of hematite, 30g of ferric sulfate and 90g of ammonium sulfate are weighed and uniformly mixed in a beaker, and the mixture is marked as a repairing agent D.
The effect of the restorative was examined by laboratory bench tests. Collecting experimental soil (S1) in the soil of the molybdenum-polluted farmland in Anhui province, naturally drying, removing impurities, grinding and sieving with a 200-mesh sieve for later use. The basic physicochemical properties of the soil are shown in table 1. The biological effectiveness analysis of molybdenum in soil adopts oxalic acid-ammonium oxalate extraction technology, and the molybdenum which can be extracted is considered to be biological effective molybdenum.
TABLE 1 basic Properties of the test soil (S1)
The experimental procedure was as follows: dividing the air-dried and sieved soil into 4 parts, each 500g, placing in a 1L beaker, and marking 1#, 2#, 3#, and 4# respectively; respectively adding a repairing agent A, a repairing agent B, a repairing agent C and a repairing agent D into No. 1, No. 2, No. 3 and No. 4, fully stirring and mixing until the mixture is uniform; then, 150mL of deionized water was added to each beaker to keep the soil wet. After 21 days of maintenance, samples were taken to analyze the content and pH value of the bio-available molybdenum in the repaired soil, and the test results are shown in Table 2. As can be seen from Table 2, the four repairing agents all have repairing effects on the bioavailable molybdenum in the soil, but the repairing effect of the repairing agent (repairing agent D) is the best, and the reduction rate of the bioavailable molybdenum is 39.8%.
TABLE 2 field molybdenum contaminated soil (S1) remediation Effect
Example 2
Weighing 30g of hematite, 30g of ferric sulfate and 90g of ammonium sulfate, uniformly mixing in a beaker, and marking as a repairing agent E; weighing 30g of hematite, 45g of ferric sulfate and 75g of ammonium sulfate, and uniformly mixing in a beaker, and marking as a repairing agent F; weighing 30G of hematite, 60G of ferric sulfate and 60G of ammonium sulfate, and uniformly mixing in a beaker, and recording as a repairing agent G; 60g of hematite, 30g of ferric sulfate and 60g of ammonium sulfate are weighed and uniformly mixed in a beaker, and the mixture is marked as a repairing agent H.
The effect of the restorative was examined by laboratory bench tests. Collecting experimental soil (S2) in the soil of the molybdenum-polluted farmland in Anhui province, naturally drying, removing impurities, grinding and sieving with a 200-mesh sieve for later use. The basic physicochemical properties of the soil are shown in table 3.
TABLE 3 basic Properties of the test soil (S2)
The experimental procedure was as follows: dividing the air-dried and sieved soil into 4 parts, each 500g, placing in a beaker of 1L, and marking with No. 5, No. 6, No. 7 and No. 8 respectively; respectively adding a repairing agent E, a repairing agent F, a repairing agent G and a repairing agent H into 5#, 6#, 7#, and 8#, fully stirring, and mixing until uniform; then, 150mL of deionized water was added to each beaker to keep the soil wet. After 21 days of maintenance, samples were taken to analyze the content and pH of the bio-available molybdenum in the repaired soil, and the test results are shown in Table 4. As can be seen from table 4, all of the 4 repair agents had the repair effect on the bioavailable molybdenum in the soil, but the repair effect of the repair agent E was the best (hematite: ferric sulfate: ammonium sulfate: 1:3), the reduction rate of bioavailable molybdenum was 28.7%, and the pH of the soil after repair was between 5.8 and 6.5.
When the weight ratio of hematite to ferric sulfate to ammonium sulfate is 1:1:3, the pH content of the soil is the lowest, and the lower the pH value is, the less the effective molybdenum content in the soil is, and the MoO is generated when the pH value of the soil is increased by one unit4 2-The concentration of the hematite and the iron sulfate is increased by 100 times, so the repairing effect is better, and meanwhile, the hydrolysate of the hematite and the iron sulfate and MoO4 2-The ferromolybdenum salt formed the most and most stable precipitate in this environment.
TABLE 4 field molybdenum contaminated soil (S2) remediation Effect
Example 3
A land plot of 10m multiplied by 10m is selected in a farmland with molybdenum pollution in Anhui province for pilot test. Collecting soil sample with depth of 0-30cm by systematic distribution, and measuring the volume weight of the soil to be 1.75g/cm3The content of molybdenum is 96mg kg-1The content of the molybdenum in the biological effective state is 18.6 mg/kg-1The soil pH was 7.5.
Adding a repairing agent into molybdenum contaminated soil of a farmland according to the mass ratio of 10:2, adding 10500kg of the repairing agent into a test cell in total, adding hematite, ferric sulfate and ammonium sulfate according to the ratio of 1:1:3 into the repairing agent, stirring the soil with the depth of 0-30cm in situ by using a small excavator, adding proper water, and sampling and analyzing the content of the molybdenum in a biological effective state after 21 days of maintenance.
Through determination, after 21 days of maintenance by adding the repairing agent, the content of the molybdenum in the biological effective state is reduced to 13.8 mg/kg < -1 >, which is reduced by 25.8%. The result proves that the repairing agent has a good repairing effect on the soil polluted by the molybdenum in the farmland, can effectively reduce the bioavailable molybdenum and reduce the harmfulness.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A molybdenum-contaminated soil remediation agent, comprising: hematite, iron sulphate and ammonium sulphate.
2. The molybdenum-contaminated soil remediation agent of claim 1, wherein said hematite is present in an amount of 15 to 40 parts, said ferric sulfate is present in an amount of 10 to 30 parts, and said ammonium sulfate is present in an amount of 50 to 80 parts by weight.
3. The molybdenum-contaminated soil remediation agent of claim 2, wherein the weight ratio of hematite to ferric sulphate to ammonium sulphate is 1:1: 3.
4. The molybdenum-contaminated soil remediation agent of claim 1, wherein said hematite comprises Fe2O3The content of the active ingredients is more than 65 percent, and the screening rate of the active ingredients after being screened by a dry screen with 20 meshes is more than 90 percent.
5. The molybdenum-contaminated soil remediation agent of any one of claims 1 to 4, wherein the molybdenum-contaminated soil remediation agent is suitable for remediation of molybdenum-contaminated soil with a pH of 3 to 12.
6. The molybdenum-contaminated soil remediation agent of any one of claims 5, wherein the molybdenum-contaminated soil remediation agent is suitable for remediation of molybdenum-contaminated soil with a pH of 6 to 9.
7. A method for restoring molybdenum-contaminated soil is characterized by comprising the following steps:
analyzing the biological available molybdenum and pH in the molybdenum-polluted soil;
adding a preset molybdenum-polluted soil remediation agent into the molybdenum-polluted soil based on the analysis result; wherein the molybdenum-contaminated soil remediation agent is the molybdenum-contaminated soil remediation agent of any one of claims 1 to 5;
stirring uniformly, moistening soil, and maintaining for 7-30 days.
8. The remediation method of claim 7 wherein the molybdenum-contaminated soil remediation agent is added in an amount of 10% to 40% by mass of the molybdenum-contaminated soil.
9. The remediation method of claim 7 wherein prior to maintenance, the soil is wetted to a soil moisture content of between 20% and 60%.
10. The remediation method of claim 7 wherein the pH of the molybdenum contaminated soil after remediation is between 5.5 and 6.5.
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