CN110076192B - In-situ remediation method for heavy metal contaminated soil - Google Patents
In-situ remediation method for heavy metal contaminated soil Download PDFInfo
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- CN110076192B CN110076192B CN201910466171.6A CN201910466171A CN110076192B CN 110076192 B CN110076192 B CN 110076192B CN 201910466171 A CN201910466171 A CN 201910466171A CN 110076192 B CN110076192 B CN 110076192B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
Abstract
The invention discloses an in-situ remediation method for heavy metal contaminated soil; the method comprises the steps of mixing chitosan and ferric salt to prepare spinning solution, obtaining chitosan/zero-valent nano-iron composite fiber through electrostatic spinning, twisting the chitosan/zero-valent nano-iron composite fiber and glass fiber by a twisting machine to form a composite adsorption rope with heavy metal adsorption and reduction capacity and certain strength, manufacturing the composite adsorption rope into a net, embedding the net into heavy metal polluted soil, taking out the net after a period of time, and completing in-situ adsorption and removal of heavy metal in the soil. The method realizes in-situ remediation of the heavy metal contaminated soil, is environment-friendly, efficient and simple to operate, and overcomes the defect that the traditional adsorbing material is difficult to separate from the soil.
Description
Technical Field
The invention relates to soil remediation, in particular to an in-situ remediation method for heavy metal contaminated soil.
Background
The heavy metal contaminated soil has the characteristics of long period, difficult treatment and the like, and the existing soil remediation method has poor effect and high cost, so the remediation of the heavy metal contaminated soil becomes a major subject in the field of environmental protection. Heavy metal pollution not only causes the change of the composition, structure and function of soil, but also can inhibit the growth of root systems of crops and photosynthesis, so that the yield of the crops is reduced and even the crops are not harvested. More importantly, heavy metals can also migrate into animals and human bodies through food chains, and seriously harm the health of the animals and the human bodies. The pollution hazards of cadmium, arsenic, blood lead and other heavy metals are commonly reported in recent years.
The in-situ treatment technology of the soil with the heavy metals exceeding the standard mainly comprises a fixed passivation technology, a plant restoration technology and an adsorbent method. The fixed passivation technology is characterized in that a fixing agent is added into soil to adjust and change the physical and chemical properties of heavy metals in the soil, so that the heavy metals generate a series of reactions such as precipitation, adsorption, ion exchange, humification and oxidation-reduction, the biological effectiveness and the mobility of the heavy metals in the soil environment are reduced, and the toxicity of the heavy metal elements to animals and plants is reduced. However, no matter which fixing agent is applied, the finally adsorbed and passivated heavy metal is remained in the soil, and the biological effectiveness can be recovered possibly along with the change of environmental conditions, so that the soil is repeatedly polluted; phytoremediation is used as a green pollution treatment means, has higher ecological benefit, but has the defects of insufficient varieties, longer time consumption and reduced yield in agriculture. The adsorbent can adsorb or convert heavy metals to allow them to migrate, but it is difficult to separate after entering the soil and may leak down to contaminate groundwater. Therefore, the research on the heavy metal adsorption material which has no secondary pollution, low price and easy separation from the soil and the treatment method thereof has more important significance for soil remediation.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provide an in-situ remediation method for heavy metal contaminated soil. The method comprises the steps of mixing chitosan and ferric salt to prepare spinning solution, obtaining chitosan/zero-valent nano-iron composite fiber through electrostatic spinning, twisting the chitosan/zero-valent nano-iron composite fiber and glass fiber by a twisting machine to form a composite adsorption rope with heavy metal adsorption and reduction capacity and certain strength, manufacturing the composite adsorption rope into a net, embedding the net into heavy metal polluted soil, taking out the net after a period of time, and completing in-situ adsorption and removal of heavy metal in the soil. The method realizes in-situ remediation of the heavy metal contaminated soil, is environment-friendly, efficient and simple to operate, and overcomes the defect that the traditional adsorbing material is difficult to separate from the soil. The invention has the advantages of high heavy metal ion adsorption efficiency, no secondary pollution and easy separation of the adsorption material from the soil.
The invention is realized by the following technical scheme:
an in-situ remediation method of heavy metal contaminated soil comprises the following specific steps:
the method comprises the following steps: dissolving chitosan in acetic acid or formic acid, adding ferric salt, introducing nitrogen to remove oxygen for 1-2 h, adding potassium borohydride into the mixed solution under mechanical stirring, and stirring for 0.5-1 h to obtain the mixed solution; adding polyvinyl alcohol into the mixed solution, stirring for 3-5 hours at 80-95 ℃ in a closed manner to prepare a spinning solution, and performing electrostatic spinning to obtain chitosan/zero-valent nano-iron composite fibers;
step two: twisting the chitosan/zero-valent nano-iron composite fiber and the glass fiber in the first step into a composite adsorption rope by using a twisting machine, and weaving the composite adsorption rope into a net shape to obtain a composite adsorption net;
step three: and (5) burying the composite adsorption net in the heavy metal polluted soil, standing for 10-30 days, and taking out the composite adsorption net from the soil to finish in-situ remediation of the soil.
The concentration of the acetic acid or the formic acid in the step one is 15 to 25 percent; the ferric salt is one or more of ferric sulfate, ferric phosphate and ferric nitrate; the stirring speed is 300-5000 r/min.
The spinning solution in the first step comprises, by weight, 15-20 parts of chitosan, 25-30 parts of acetic acid or formic acid, 10-15 parts of ferric salt, 3-4 parts of potassium borohydride and 60-80 parts of polyvinyl alcohol.
In the electrostatic spinning process in the first step, the humidity is 40-50%, the voltage is 25-30 kV, and the distance from the needle head to the receiving plate is 18-25 cm.
In the second step, the mass ratio of the chitosan/zero-valent nano-iron composite fiber to the glass fiber is 1.5: 1-2.5: 1.
And in the second step, the twisting machine adopts a ring twisting machine, the diameter of the twisted composite adsorption rope is 2-4 mm, and the diameter of the mesh of the composite net is 2-20 mm.
The heavy metal is one or more of chromium, cadmium, arsenic, mercury and lead.
The depth of the composite adsorption net buried in the soil surface is 20-30 cm; the water content of the soil is 40-90%, the pH value of the soil is 3-7, or the pH value of the soil is 4-7.
Compared with the prior art, the invention has the following advantages and effects:
the presence of a large amount of-NH in chitosan2Functional groups such as-OH and the like have charge attraction effect and chelation effect on heavy metal ions; the zero-valent nano iron has small particle size, super large specific surface area, high reaction activity, strong reducibility and adsorbability, and has strong removal capability on heavy metal ions.
The method comprises the steps of mixing chitosan and ferric salt to prepare spinning solution, carrying out electrostatic spinning to obtain chitosan/zero-valent nano-iron composite fibers, twisting the chitosan/zero-valent nano-iron composite fibers and glass fibers by a twisting machine to obtain composite adsorption ropes with heavy metal adsorption and reduction capacity and certain strength, weaving the composite adsorption ropes into nets, embedding the composite adsorption ropes into soil with heavy metals exceeding the standard, taking out the composite adsorption ropes after a period of time, and completing in-situ adsorption and removal of the heavy metals in the soil. The method realizes in-situ remediation of the heavy metal contaminated soil, is environment-friendly, efficient and simple to operate, and solves the problem that the traditional adsorbing material is difficult to separate from the soil.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
(1) Dissolving chitosan in a 15% acetic acid solution, adding ferric sulfate, introducing nitrogen to remove oxygen for 1h, adding potassium borohydride into the mixed solution under mechanical stirring (300 revolutions per minute), stirring at a high speed (3000 revolutions per minute) for 1h to obtain a mixed solution, adding polyvinyl alcohol into the mixed solution, and stirring in a closed manner at 85 ℃ for 3h (500 revolutions per minute) after the addition is finished to prepare a spinning solution, wherein the spinning solution comprises 15 parts by weight of chitosan, 28 parts by weight of acetic acid, 15 parts by weight of ferric sulfate, 4 parts by weight of potassium borohydride and 80 parts by weight of polyvinyl alcohol. The electrostatic spinning humidity is 40%, the voltage is 25kV, the distance from the needle head to the receiving plate is 19cm, and the chitosan/zero-valent nano-iron composite fiber is obtained;
(2) compositely twisting the chitosan/zero-valent nano-iron composite fiber and the glass fiber in the step (1) into a composite adsorption rope with the diameter of 2mm by adopting a ring twisting machine according to the mass ratio of 1.5:1, and making a net with the diameter of 2 mm;
(3) burying the composite adsorption net in the step (2) into soil (with the water content of 70% and the pH value of 5) polluted by chromium (3000ppm), and standing for 15 days, wherein the depth of the composite adsorption net buried in the soil surface is 25 cm;
and taking out the composite adsorption net adsorbing the heavy metals from the soil to finish the in-situ remediation of the soil. The total amount of chromium in the soil was determined according to standard HJ491, with a residual amount of 200ppm and a removal rate of 93%.
Example 2
(1) Dissolving chitosan in 20% formic acid solution, adding iron phosphate into the solution, introducing nitrogen to remove oxygen for 2 hours, adding potassium borohydride into the mixed solution under mechanical stirring (500 revolutions per minute), stirring at high speed (5000 revolutions per minute) for 1 hour to obtain a mixed solution, adding polyvinyl alcohol into the mixed solution, and after the addition is finished, stirring in a closed manner at 90 ℃ for 3.5 hours (1000 revolutions per minute) to prepare a spinning solution, wherein the spinning solution comprises, by weight, 17 parts of chitosan, 30 parts of formic acid, 13 parts of iron phosphate, 3 parts of potassium borohydride and 75 parts of polyvinyl alcohol. The electrostatic spinning humidity is 45%, the voltage is 28kV, the distance from the needle head to the receiving plate is 22cm, and the chitosan/zero-valent nano-iron composite fiber is obtained;
(2) and (2) compositely twisting the chitosan/zero-valent nano-iron composite fiber and the glass fiber in the step (1) into a composite adsorption rope with the diameter of 3mm by adopting a ring twisting machine according to the mass ratio of 2.5:1, and manufacturing a net with the diameter of 5 mm.
(3) Burying the composite adsorption net in the step (2) into soil (with the water content of 60% and the pH value of 4) polluted by cadmium (10ppm), and standing for 18 days, wherein the depth of the composite adsorption net buried in the soil surface is 22 cm;
and taking out the composite adsorption net adsorbing the heavy metals from the soil to finish the in-situ remediation of the soil. The total amount of cadmium in the soil is measured according to the standard GB/T17141, the residual quantity is 1ppm, and the removal rate is 90%.
Example 3
(1) Dissolving chitosan in 25% acetic acid solution, adding ferric sulfate, introducing nitrogen to remove oxygen for 1h, adding potassium borohydride into the mixed solution under mechanical stirring (1000 revolutions per minute), stirring at high speed (4000 revolutions per minute) for 1h to obtain mixed solution, adding polyvinyl alcohol into the mixed solution, and stirring in a closed manner at 95 ℃ for 5h (400 revolutions per minute) after the addition is finished to prepare spinning solution, wherein the spinning solution comprises, by weight, 19 parts of chitosan, 25 parts of acetic acid, 12 parts of ferric sulfate, 4 parts of potassium borohydride and 70 parts of polyvinyl alcohol. The electrostatic spinning humidity is 50%, the voltage is 25kV, the distance from the needle to the receiving plate is 23cm, and the chitosan/zero-valent nano-iron composite fiber is obtained;
(2) compositely twisting the chitosan/zero-valent nano-iron composite fiber and the glass fiber in the step (1) into a composite adsorption rope with the diameter of 4mm by adopting a ring twisting machine according to the mass ratio of 2:1, and making a net with the diameter of 10 mm;
(3) burying the composite adsorption net in the step (2) into arsenic polluted (300ppm) soil (with the water content of 40% and the pH value of 4), and standing for 22 days, wherein the depth of the composite adsorption net buried in the soil surface is 25 cm;
(4) and taking out the composite adsorption net adsorbing the heavy metals from the soil to finish the in-situ remediation of the soil. The total amount of arsenic in the soil is measured according to the standard GB/T22105.2, the residual quantity is 20ppm, and the removal rate is 93%.
Example 4
(1) Dissolving chitosan in 25% formic acid solution, adding ferric nitrate, introducing nitrogen to remove oxygen for 1.5h, adding potassium borohydride into the mixed solution under mechanical stirring (2000 revolutions per minute), stirring at high speed (3500 revolutions per minute) for 0.5h to obtain a mixed solution, adding polyvinyl alcohol into the mixed solution, and after the addition is finished, stirring in a sealed manner at 85 ℃ for 4h (600 revolutions per minute) to prepare a spinning solution, wherein the spinning solution comprises, by weight, 20 parts of chitosan, 30 parts of formic acid, 15 parts of ferric nitrate, 4 parts of potassium borohydride and 80 parts of polyvinyl alcohol. The electrostatic spinning humidity is 40%, the voltage is 29kV, and the distance from the needle to the receiving plate is 25cm, so that the chitosan/zero-valent nano-iron composite fiber is obtained;
(2) compositely twisting the chitosan/zero-valent nano-iron composite fiber and the glass fiber in the step (1) into a composite adsorption rope with the diameter of 3mm by adopting a ring twisting machine according to the mass ratio of 1.5:1, and making a net with the diameter of 8 mm;
(3) burying the composite adsorption net in the step (2) into soil (with the water content of 40% and the pH value of 5) polluted by mercury (10ppm), and standing for 25 days, wherein the depth of the composite adsorption net buried in the soil surface is 30 cm;
(4) and taking out the composite adsorption net adsorbing the heavy metals from the soil to finish the in-situ remediation of the soil. The total mercury content in the soil is measured according to the standard GB/T22105.1, the residual quantity is 1ppm, and the removal rate is 90%.
Example 5
(1) Dissolving chitosan in 21% formic acid solution, adding iron phosphate into the formic acid solution, introducing nitrogen to remove oxygen for 2 hours, adding potassium borohydride into the mixed solution under mechanical stirring (700 revolutions per minute), stirring at high speed (4500 revolutions per minute) for 0.5 hour to obtain a mixed solution, adding polyvinyl alcohol into the mixed solution, and stirring in a closed manner at 95 ℃ for 3 hours (700 revolutions per minute) after the addition is finished to prepare a spinning solution, wherein the spinning solution comprises, by weight, 19 parts of chitosan, 28 parts of formic acid, 13 parts of iron phosphate, 3 parts of potassium borohydride and 70 parts of polyvinyl alcohol. The electrostatic spinning humidity is 45%, the voltage is 26kV, the distance from the needle head to the receiving plate is 19cm, and the chitosan/zero-valent nano-iron composite fiber is obtained;
(2) compositely twisting the chitosan/zero-valent nano-iron composite fiber and the glass fiber in the step (1) into a composite adsorption rope with the diameter of 3mm by adopting a ring twisting machine according to the mass ratio of 1.8:1, and making a net with the diameter of 20 mm;
(3) burying the composite adsorption net in the step (2) into lead polluted (1000ppm) soil (with water content of 80% and pH value of 6), and standing for 24 days, wherein the depth of the composite adsorption net buried in the soil surface is 25 cm;
(4) and taking out the composite adsorption net adsorbing the heavy metals from the soil to finish the in-situ remediation of the soil. The total amount of lead in the soil is measured according to the standard GB/T17141, the residual quantity is 80ppm, and the removal rate is 92%.
Example 6
(1) Dissolving chitosan in a 23% acetic acid solution, adding ferric sulfate, introducing nitrogen to remove oxygen for 1h, adding potassium borohydride into the mixed solution under mechanical stirring (500 revolutions per minute), stirring at a high speed (4500 revolutions per minute) for 1h to obtain a mixed solution, adding polyvinyl alcohol into the mixed solution, and stirring in a closed manner at 90 ℃ for 4h (800 revolutions per minute) after the addition is finished to prepare a spinning solution, wherein the spinning solution comprises 18 parts by weight of chitosan, 26 parts by weight of acetic acid, 14 parts by weight of ferric sulfate, 4 parts by weight of potassium borohydride and 75 parts by weight of polyvinyl alcohol. The electrostatic spinning humidity is 50%, the voltage is 28kV, the distance from the needle head to the receiving plate is 22cm, and the chitosan/zero-valent nano-iron composite fiber is obtained;
(2) twisting the chitosan/zero-valent nano-iron composite fiber and the glass fiber in the step (1) by a ring twisting machine according to the mass ratio of 2.2:1 to form a composite adsorption rope with the diameter of 2mm, and forming a net with the diameter of 15 mm;
(3) burying the composite adsorption net in the step (2) into soil (with the water content of 90% and the pH value of 7) polluted by cadmium and lead (respectively 10ppm and 1000ppm), and standing for 28 days, wherein the depth of the composite adsorption net buried in the soil surface is 27 cm;
(4) and taking out the composite adsorption net adsorbing the heavy metals from the soil to finish the in-situ remediation of the soil. The total amount of cadmium and lead in the soil is measured according to the standard GB/T17141, the residual amounts are 1ppm and 100ppm respectively, and the removal rate is 90%.
As described above, the present invention can be preferably realized.
The embodiments of the present invention are not limited to the above-described embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.
Claims (4)
1. An in-situ remediation method for heavy metal contaminated soil is characterized by comprising the following specific steps:
the method comprises the following steps: dissolving chitosan in acetic acid or formic acid, adding ferric salt, introducing nitrogen to remove oxygen for 1-2 h, adding potassium borohydride into the mixed solution under mechanical stirring, and stirring for 0.5-1 h to obtain the mixed solution; adding polyvinyl alcohol into the mixed solution, stirring for 3-5 hours at 80-95 ℃ in a closed manner to prepare a spinning solution, and performing electrostatic spinning to obtain the chitosan zero-valent nano-iron composite fiber;
step two: twisting the chitosan zero-valent nano-iron composite fiber and the glass fiber in the first step into a composite adsorption rope by using a twisting machine, and weaving the composite adsorption rope into a net shape to obtain a composite adsorption net;
step three: burying the composite adsorption net in the heavy metal polluted soil, placing for 10-30 days, and taking out the composite adsorption net from the soil to finish in-situ remediation of the soil;
the depth of the composite adsorption net buried in the soil surface is 20-30 cm; the water content of the soil is 40-90%, and the pH value of the soil is 3-7;
the concentration of the acetic acid or the formic acid in the first step is 15% -25%; the ferric salt is one or more of ferric sulfate, ferric phosphate and ferric nitrate; the stirring speed is 300-5000 revolutions per minute;
the spinning solution in the first step comprises, by weight, 15-20 parts of chitosan, 25-30 parts of acetic acid or formic acid, 10-15 parts of ferric salt, 3-4 parts of potassium borohydride and 60-80 parts of polyvinyl alcohol;
and in the second step, the mass ratio of the chitosan zero-valent nano-iron composite fiber to the glass fiber is 1.5: 1-2.5: 1.
2. The in-situ remediation method of heavy metal contaminated soil according to claim 1, wherein: in the electrostatic spinning process in the first step, the humidity is 40-50%, the voltage is 25-30 kV, and the distance from the needle head to the receiving plate is 18-25 cm.
3. The in-situ remediation method of heavy metal contaminated soil according to claim 2, wherein: and in the second step, a ring twisting machine is adopted as the twisting machine, the diameter of the twisted composite adsorption rope is 2-4 mm, and the diameter of the mesh of the composite net is 2-20 mm.
4. The in-situ remediation method of heavy metal contaminated soil according to claim 3, wherein: the heavy metal is one or more of chromium, cadmium, arsenic, mercury and lead.
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