CN114804319A - Iron-based nano material for in-situ remediation of heavy metal polluted underground water and preparation method and application thereof - Google Patents
Iron-based nano material for in-situ remediation of heavy metal polluted underground water and preparation method and application thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 185
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 57
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 56
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 43
- 238000005067 remediation Methods 0.000 title claims abstract description 25
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 59
- 230000003647 oxidation Effects 0.000 claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 39
- 239000003112 inhibitor Substances 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims description 84
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 70
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 70
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 70
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 70
- 239000000243 solution Substances 0.000 claims description 58
- 239000000725 suspension Substances 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000003673 groundwater Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 230000005389 magnetism Effects 0.000 abstract description 6
- 238000003911 water pollution Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 43
- 239000000843 powder Substances 0.000 description 40
- 230000000052 comparative effect Effects 0.000 description 18
- 238000004806 packaging method and process Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005034 decoration Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000003895 groundwater pollution Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46176—Galvanic cells
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides an iron-based nano material for in-situ remediation of heavy metal polluted underground water, and a preparation method and application thereof, and belongs to the technical field of underground water pollution treatment. The iron-based nano material is prepared from nano zero-valent iron, nano ferroferric oxide, an oxidation inhibitor and activated carbon, wherein the mass ratio of the nano zero-valent iron to the nano ferroferric oxide to the oxidation inhibitor to the activated carbon is 10: 1.5-2.5: 3-7. The iron-based nano material provided by the invention solves the problems that nano zero-valent iron is easy to oxidize, agglomerate and have weakened magnetism.
Description
Technical Field
The invention belongs to the technical field of groundwater pollution treatment, and particularly relates to an iron-based nano material for in-situ remediation of heavy metal polluted groundwater, and a preparation method and application thereof.
Background
The main difficulties of the remediation of the heavy metal polluted underground water are as follows: (1) the water flow is large, and the requirement is difficult to meet by adopting a common wastewater ex-situ treatment method; (2) compared with the common sewage, the heavy metal content in the underground water is lower, and is generally within 1 mg/L. The common method has large material usage amount and high cost. (3) Most underground water flows in a complex direction, the effective treatment is difficult to obtain by adopting the traditional in-situ remediation method, and the treated waste residues are difficult to recover. And heavy metal pollution is caused to be repeated continuously when the water is left underground.
The method has the advantages that the method adopts the nano zero-valent iron material to treat the groundwater: (1) the activity of the material is far higher than that of the existing general material, so that the concentration of heavy metal in underground water can reach the standard, and the use amount of the material is greatly reduced; (2) the material has certain magnetism, and is convenient to recover through magnetism after being processed. However, the direct use of the nano zero-valent iron material has problems: (1) the material is extremely oxidized and difficult to store; (2) the material is easy to agglomerate, so that the material is easy to precipitate after being added into water; (3) after the material is used, the magnetism of the material is weakened to some extent due to the oxidation of Fe.
Disclosure of Invention
In view of the above, the invention aims to provide an iron-based nano material for in-situ remediation of heavy metal polluted underground water, and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides an iron-based nano material for in-situ remediation of heavy metal polluted underground water, which is prepared from nano zero-valent iron, nano ferroferric oxide, an oxidation inhibitor and activated carbon, wherein the mass ratio of the nano zero-valent iron to the nano ferroferric oxide to the oxidation inhibitor to the activated carbon is 10: 1.5-2.5: 3-7.
Preferably, the oxidation inhibitor comprises one or more of carboxymethyl cellulose, chitosan and soluble starch.
The invention also provides a preparation method of the iron-based nano material in the technical scheme, which comprises the following steps:
1) dissolving the oxidation inhibitor in water to obtain an oxidation inhibitor solution;
2) dispersing the nano zero-valent iron to obtain a nano zero-valent iron suspension; dispersing the nano ferroferric oxide to obtain a nano ferroferric oxide suspension; mixing the nano zero-valent iron suspension, the nano ferroferric oxide suspension and the antioxidant solution obtained in the step 1) to obtain a mixed solution;
3) mixing the mixed suspension obtained in the step 2) with activated carbon, and performing solid-liquid separation to obtain a solid which is an iron-based nano material;
the mass ratio of the nano zero-valent iron to the nano ferroferric oxide to the antioxidant to the active carbon is 10: 1.5-2.5: 3-7.
Preferably, the temperature of the water in the step 1) is 40-80 ℃.
Preferably, the mass ratio of the water and the oxidation inhibitor in the step 1) is 3-8: 1.
Preferably, the mass ratio of the water to the oxidation inhibitor is 5: 1.
Preferably, the mixing in the step 2) and the step 3) is carried out under stirring, and the stirring speed is 100-300 rpm.
The invention also provides application of the iron-based nano material in the technical scheme in-situ remediation of heavy metal polluted underground water.
Preferably, the application comprises: the total mass of the heavy metal in the groundwater is 1g/m 3 The addition amount of the iron-based nano material is 10g/m 3 。
Preferably, the heavy metal comprises one or more of zinc, lead and arsenic.
The invention provides an iron-based nano material for in-situ remediation of heavy metal polluted underground water, which is prepared from nano zero-valent iron, nano ferroferric oxide, an oxidation inhibitor and activated carbon, wherein the mass ratio of the nano zero-valent iron to the nano ferroferric oxide to the carboxymethyl cellulose to the activated carbon is 10: 1.5-2.5: 3-7.
The mechanism of the problem solved by the invention is as follows:
(1) the nanometer zero-valent iron and the nanometer ferroferric oxide are mixed for use, and the problem of weakened magnetism of the material after use can be solved due to the stability and magnetism of the ferroferric oxide, so that the recovery is convenient. In addition, the iron and the ferroferric oxide form a micro battery in the using process, so that the using activity of the material can be further improved.
(2) Adopts an oxidation inhibitor to mainly solve the problem of material oxidation. Firstly, dissolving the oxidation inhibitor, then adding the nano zero-valent iron and the nano ferroferric oxide, and enabling the oxidation inhibitor to cover the surface of the material, thereby preventing the material from directly contacting with air and reducing the oxidation failure of the material.
(3) The method adopts the active carbon, and the main effects of the active carbon comprise three aspects, wherein one of the three aspects is used as a carrier, so that the agglomeration of nano materials is effectively reduced; secondly, the micro-battery can be formed with the nano zero-valent iron to improve the activity of the material; thirdly, the suspension time of the material in water can be improved, so that the contact chance of the material and heavy metal ions in the water is improved, and the removal capacity of the material is further improved.
Detailed Description
The invention provides an iron-based nano material for in-situ remediation of heavy metal polluted underground water, which is prepared from nano zero-valent iron, nano ferroferric oxide, an oxidation inhibitor and activated carbon, wherein the mass ratio of the nano zero-valent iron to the nano ferroferric oxide to the oxidation inhibitor to the activated carbon is 10: 1.5-2.5: 3-7. In the present invention, the oxidation inhibitor preferably includes one or more of carboxymethyl cellulose, chitosan and soluble starch. The sources of the raw materials are not particularly limited in the present invention, and conventional commercially available products can be used.
The invention also provides a preparation method of the iron-based nano material in the technical scheme, which comprises the following steps:
1) dissolving the oxidation inhibitor in water to obtain an oxidation inhibitor solution;
2) dispersing the nano zero-valent iron to obtain a nano zero-valent iron suspension; dispersing the nano ferroferric oxide to obtain a nano ferroferric oxide suspension; mixing the nano zero-valent iron suspension, the nano ferroferric oxide suspension and the antioxidant solution obtained in the step 1) to obtain a mixed solution;
3) mixing the mixed suspension obtained in the step 2) with activated carbon, and carrying out solid-liquid separation to obtain a solid which is an iron-based nano material;
the mass ratio of the nano zero-valent iron to the nano ferroferric oxide to the antioxidant to the active carbon is 10: 1.5-2.5: 3-7.
In the invention, the mass ratio of the nano zero-valent iron to the nano ferroferric oxide to the oxidation inhibitor to the active carbon is 10:2:5: 5.
The oxidation inhibitor is dissolved in water to obtain an oxidation inhibitor solution. In the invention, the mass ratio of the water to the oxidation inhibitor is preferably 3-8: 1, and more preferably 5: 1. In the invention, when the mass ratio of the water to the oxidation inhibitor is lower than 3:1, the oxidation inhibitor (carboxymethyl cellulose) solution is viscous and is difficult to be fully mixed. When the mass ratio of the water to the oxidation inhibitor exceeds 8:1, the content of the water is too high, so that the solution of the oxidation inhibitor (carboxymethyl cellulose) is too thin, and the carboxymethyl cellulose coated on the surface of the nano material is too little to play a role in protecting the material. In the invention, the temperature of the water is preferably 40-80 ℃, and the dissolution of the oxidation inhibitor is accelerated.
Dispersing the nano zero-valent iron to obtain a nano zero-valent iron suspension; dispersing the nano ferroferric oxide to obtain a nano ferroferric oxide suspension; and mixing the nano zero-valent iron suspension, the nano ferroferric oxide suspension and the obtained oxidation inhibitor solution to obtain a mixed solution.
The invention carries out dispersion treatment on the nanometer zero-valent iron and the nanometer ferroferric oxide, the used dispersing agent is not specially limited, and the technical personnel in the field can adopt the conventional reagent, such as polyacrylamide. The using amount of the dispersing agent is not particularly limited, and the nano zero-valent iron and the nano ferroferric oxide can be dispersed. In the present invention, the mixing is performed under stirring, and the stirring speed is preferably 100 to 300 rpm.
The obtained mixed suspension is mixed with activated carbon, and solid-liquid separation is carried out to obtain the solid which is the iron-based nano material. In the present invention, the mixing is performed under stirring, and the stirring speed is preferably 100 to 300 rpm. The method for solid-liquid separation is not particularly limited, and the method can be carried out by a person skilled in the art according to the conventional method. After solid-liquid separation, the obtained mud-like material is an iron-based nano material, and the water content is 50 percent by mass. In the present invention, the iron-based nanomaterial is preferably hermetically packaged to prevent oxidative failure.
The invention also provides application of the iron-based nano material in the technical scheme in-situ remediation of heavy metal polluted underground water. In the present invention, the application includes: the total mass of the heavy metal in the groundwater is 1g/m 3 In the case of the iron-based nanomaterial, the addition amount of the iron-based nanomaterial is 10g/m 3 . In the present invention, the heavy metal preferably includes one or more of zinc, lead and arsenic.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The preparation method of the iron-based nano material for in-situ remediation of the heavy metal polluted underground water comprises the following steps:
(1) firstly, preparing water with the temperature of 50 ℃, adding carboxymethyl cellulose according to the mass ratio of the water to the carboxymethyl cellulose of 3:1, continuously stirring at the stirring speed of 200rpm until the carboxymethyl cellulose is completely dissolved to obtain a carboxymethyl cellulose solution;
(2) respectively dispersing nano zero-valent iron powder and nano ferroferric oxide powder, then respectively adding the dispersed nano zero-valent iron suspension and nano ferroferric oxide suspension into a carboxymethyl cellulose solution, and uniformly stirring at the stirring speed of 200rpm to obtain a mixed suspension;
(3) then, adding activated carbon into the mixed suspension, and fully stirring at the stirring speed of 200 rpm;
carrying out nano zero-valent iron powder, nano ferroferric oxide powder, carboxymethyl cellulose and active carbon according to the mass ratio of 10:2:5: 5;
(4) and after stirring is finished, rapidly carrying out solid-liquid separation on the solution to obtain the iron-based nano material, wherein the water content is 50%, and hermetically packaging to prevent the material from being oxidized and losing efficacy.
Example 2
The preparation method of the iron-based nano material for in-situ remediation of the heavy metal polluted underground water comprises the following steps:
(1) firstly, preparing water with the temperature of 50 ℃, adding carboxymethyl cellulose according to the mass ratio of the water to the carboxymethyl cellulose of 8:1, continuously stirring at the stirring speed of 200rpm until the carboxymethyl cellulose is completely dissolved to obtain a carboxymethyl cellulose solution;
(2) respectively dispersing nano zero-valent iron powder and nano ferroferric oxide powder, then respectively adding the dispersed nano zero-valent iron suspension and nano ferroferric oxide suspension into a carboxymethyl cellulose solution, and uniformly stirring at the stirring speed of 200rpm to obtain a mixed suspension;
(3) then, adding activated carbon into the mixed suspension, and fully stirring at the stirring speed of 200 rpm;
carrying out nano zero-valent iron powder, nano ferroferric oxide powder, carboxymethyl cellulose and active carbon according to the mass ratio of 10:2:5: 5;
(4) and after stirring is finished, rapidly carrying out solid-liquid separation on the solution to obtain the iron-based nano material, wherein the water content is 50%, and hermetically packaging to prevent the material from being oxidized and losing efficacy.
Example 3
The preparation method of the iron-based nano material for in-situ remediation of the heavy metal polluted underground water comprises the following steps:
(1) firstly, preparing water with the temperature of 50 ℃, adding carboxymethyl cellulose according to the mass ratio of the water to the carboxymethyl cellulose of 5:1, continuously stirring at the stirring speed of 200rpm until the carboxymethyl cellulose is completely dissolved to obtain a carboxymethyl cellulose solution;
(2) respectively dispersing nano zero-valent iron powder and nano ferroferric oxide powder, then respectively adding the dispersed nano zero-valent iron suspension and nano ferroferric oxide suspension into a carboxymethyl cellulose solution, and uniformly stirring at the stirring speed of 200rpm to obtain a mixed suspension;
(3) then, adding activated carbon into the mixed suspension, and fully stirring at the stirring speed of 200 rpm;
carrying out nano zero-valent iron powder, nano ferroferric oxide powder, carboxymethyl cellulose and active carbon according to the mass ratio of 10:2:5: 5;
(4) and after stirring is finished, rapidly carrying out solid-liquid separation on the solution to obtain the iron-based nano material, wherein the water content is 50%, and hermetically packaging to prevent the material from being oxidized and losing efficacy.
Example 4
The preparation method of the iron-based nano material for in-situ remediation of the heavy metal polluted underground water comprises the following steps:
(1) firstly, preparing water with the temperature of 50 ℃, adding carboxymethyl cellulose according to the mass ratio of the water to the carboxymethyl cellulose of 5:1, continuously stirring at the stirring speed of 200rpm until the carboxymethyl cellulose is completely dissolved to obtain a carboxymethyl cellulose solution;
(2) respectively dispersing nano zero-valent iron powder and nano ferroferric oxide powder, then respectively adding the dispersed nano zero-valent iron solution and nano ferroferric oxide solution into a carboxymethyl cellulose solution, and uniformly stirring at the stirring speed of 200rpm to obtain a mixed solution;
(3) then, adding activated carbon into the mixed solution, and fully stirring at the stirring speed of 200 rpm;
carrying out nano zero-valent iron powder, nano ferroferric oxide powder, carboxymethyl cellulose and active carbon according to the mass ratio of 10:1.5:3: 3;
(4) and after stirring is finished, rapidly carrying out solid-liquid separation on the solution to obtain the iron-based nano material, wherein the water content is 50%, and hermetically packaging to prevent the material from being oxidized and losing efficacy.
Example 5
The preparation method of the iron-based nano material for in-situ remediation of the heavy metal polluted underground water comprises the following steps:
(1) firstly, preparing water with the temperature of 50 ℃, adding carboxymethyl cellulose according to the mass ratio of the water to the carboxymethyl cellulose of 5:1, continuously stirring at the stirring speed of 200rpm until the carboxymethyl cellulose is completely dissolved to obtain a carboxymethyl cellulose solution;
(2) respectively dispersing nano zero-valent iron powder and nano ferroferric oxide powder, then respectively adding the dispersed nano zero-valent iron solution and nano ferroferric oxide solution into a carboxymethyl cellulose solution, and uniformly stirring at the stirring speed of 200rpm to obtain a mixed solution;
(3) then, adding activated carbon into the mixed solution, and fully stirring at the stirring speed of 200 rpm;
carrying out nano zero-valent iron powder, nano ferroferric oxide powder, carboxymethyl cellulose and active carbon according to the mass ratio of 10:2.5:7: 7;
(5) and after stirring is finished, rapidly carrying out solid-liquid separation on the solution to obtain the iron-based nano material, wherein the water content is 50%, and hermetically packaging to prevent the material from being oxidized and losing efficacy.
Comparative example 1
The preparation method of the iron-based nano material for in-situ remediation of the heavy metal polluted underground water comprises the following steps:
(1) firstly, preparing water with the temperature of 50 ℃, adding carboxymethyl cellulose according to the mass ratio of the water to the carboxymethyl cellulose of 5:1, continuously stirring at the stirring speed of 200rpm until the carboxymethyl cellulose is completely dissolved to obtain a carboxymethyl cellulose solution;
(2) dispersing the nano zero-valent iron powder, adding the dispersed nano zero-valent iron solution into the carboxymethyl cellulose solution, and uniformly stirring at the stirring speed of 200rpm to obtain a mixed solution;
(3) then adding activated carbon into the mixed solution, and fully stirring at the stirring speed of 200 rpm;
performing nano zero-valent iron powder, carboxymethyl cellulose and active carbon according to the mass ratio of 10:5: 5;
(4) and after stirring is finished, rapidly carrying out solid-liquid separation on the solution to obtain the iron-based nano material, wherein the water content is 50%, and hermetically packaging to prevent the material from being oxidized and losing efficacy.
Comparative example 2
The preparation method of the iron-based nano material for in-situ remediation of the heavy metal polluted underground water comprises the following steps:
(1) respectively dispersing nano zero-valent iron powder and nano ferroferric oxide powder, and then uniformly stirring the dispersed nano zero-valent iron solution and nano ferroferric oxide solution at the stirring speed of 200rpm to obtain a mixed solution;
(2) then, adding activated carbon into the mixed solution, and fully stirring at the stirring speed of 200 rpm;
carrying out nano zero-valent iron powder, nano ferroferric oxide powder and active carbon according to the mass ratio of 10:2: 5;
(3) and after stirring is finished, rapidly carrying out solid-liquid separation on the solution to obtain the iron-based nano material, wherein the water content is 50%, and hermetically packaging to prevent the material from being oxidized and losing efficacy.
Comparative example 3
The preparation method of the iron-based nano material for in-situ remediation of the heavy metal polluted underground water comprises the following steps:
(1) firstly, preparing water with the temperature of 50 ℃, adding carboxymethyl cellulose according to the mass ratio of the water to the carboxymethyl cellulose of 5:1, continuously stirring at the stirring speed of 200rpm until the carboxymethyl cellulose is completely dissolved to obtain a carboxymethyl cellulose solution;
(2) respectively dispersing nano zero-valent iron powder and nano ferroferric oxide powder, then respectively adding the dispersed nano zero-valent iron solution and nano ferroferric oxide solution into a carboxymethyl cellulose solution, and uniformly stirring at the stirring speed of 200rpm to obtain a mixed solution;
carrying out nano zero-valent iron powder, nano ferroferric oxide powder and carboxymethyl cellulose according to the mass ratio of 10:2: 5;
(3) and after stirring is finished, rapidly carrying out solid-liquid separation on the solution to obtain the iron-based nano material, wherein the water content is 50%, and hermetically packaging to prevent the material from being oxidized and losing efficacy.
Comparative example 4
The preparation method of the iron-based nano material for in-situ remediation of the heavy metal polluted underground water comprises the following steps:
(1) firstly, preparing water with the temperature of 50 ℃, adding carboxymethyl cellulose according to the mass ratio of the water to the carboxymethyl cellulose of 2:1, continuously stirring at the stirring speed of 200rpm until the carboxymethyl cellulose is completely dissolved to obtain a carboxymethyl cellulose solution;
(2) respectively dispersing nano zero-valent iron powder and nano ferroferric oxide powder, then respectively adding the dispersed nano zero-valent iron solution and nano ferroferric oxide solution into a carboxymethyl cellulose solution, and uniformly stirring at a stirring speed of 200rpm to obtain a mixed solution;
(3) then, adding activated carbon into the mixed solution, and fully stirring at the stirring speed of 200 rpm;
carrying out nano zero-valent iron powder, nano ferroferric oxide powder, carboxymethyl cellulose and active carbon according to the mass ratio of 10:2:5: 5;
(4) and after stirring is finished, rapidly carrying out solid-liquid separation on the solution to obtain the iron-based nano material, wherein the water content is 50%, and hermetically packaging to prevent the material from being oxidized and losing efficacy.
Comparative example 5
The preparation method of the iron-based nano material for in-situ remediation of the heavy metal polluted underground water comprises the following steps:
(1) firstly, preparing water with the temperature of 50 ℃, adding carboxymethyl cellulose according to the mass ratio of the water to the carboxymethyl cellulose of 9:1, continuously stirring at the stirring speed of 200rpm until the carboxymethyl cellulose is completely dissolved to obtain a carboxymethyl cellulose solution;
(2) respectively dispersing nano zero-valent iron powder and nano ferroferric oxide powder, then respectively adding the dispersed nano zero-valent iron solution and nano ferroferric oxide solution into a carboxymethyl cellulose solution, and uniformly stirring at the stirring speed of 200rpm to obtain a mixed solution;
(3) then, adding activated carbon into the mixed solution, and fully stirring at the stirring speed of 200 rpm;
carrying out nano zero-valent iron powder, nano ferroferric oxide powder, carboxymethyl cellulose and active carbon according to the mass ratio of 10:2:5: 5;
(4) and after stirring is finished, rapidly carrying out solid-liquid separation on the solution to obtain the iron-based nano material, wherein the water content is 50%, and hermetically packaging to prevent the material from being oxidized and losing efficacy.
Carrying out in-situ remediation experiments on the heavy metal polluted underground water by the iron-based nano materials obtained in the examples 1-5 and the comparative examples 1-5, wherein the experimental method comprises the following steps: the using amount of the heavy metal polluted underground water is 1L, the total amount of the heavy metals is 2.64mg/L, the adding amount of the iron-based nano material is 26.4mg/L, the reaction time is 5min, an inductively coupled plasma mass spectrometer (ICP-MS7500) is adopted to detect the metal content of the heavy metal polluted underground water, and the detection process comprises the following steps: weighing 1L of underground water polluted by heavy metals, weighing 26.4mg of materials, adding the materials, mechanically stirring (the stirring speed is 200rpm), timing from the beginning of stirring, taking 10ml of water sample after stirring for 5min, taking supernate to detect the content of the heavy metals after centrifugally separating the water sample, wherein the detection equipment is an inductively coupled plasma mass spectrometer (ICP-MS7500), and the result is shown in Table 1.
TABLE 1 results of removing heavy metal contaminated groundwater
| Zinc (mg/L) | Lead (mg/L) | Arsenic (mg/L) | |
| Raw Water composition | 1.8 | 0.15 | 0.69 |
| Example 1 | 0.10 | 0.07 | 0.009 |
| Example 2 | 0.11 | 0.08 | 0.01 |
| Example 3 | 0.09 | 0.05 | 0.008 |
| Example 4 | 0.11 | 0.09 | 0.015 |
| Example 5 | 0.12 | 0.09 | 0.012 |
| Comparative example 1 | 0.16 | 0.11 | 0.097 |
| Comparative example 2 | 0.51 | 0.14 | 0.32 |
| Comparative example 3 | 0.24 | 0.12 | 0.18 |
| Comparative example 4 | 0.42 | 0.14 | 0.21 |
| Comparative example 5 | 0.20 | 0.10 | 0.10 |
As can be derived from table 1, when water: when the carboxymethyl cellulose is added according to the ratio of (3-8) to (1), the oxidation prevention effect on the nano zero-valent iron is better, and in comparative examples 4 and 5, the removal effect of the material in the use process can be influenced due to over-thick or over-thin carboxymethyl cellulose solution. While comparative example 2, in which no carboxymethyl cellulose solution was added, had a poorer effect on removing heavy metals.
The active carbon in the iron-based nano material mainly plays a role of a carrier, and the removal effect is obviously weakened because the active carbon is not added in the comparative example 3, which is mainly because the nano particles in the material are agglomerated and the activity of the material is weakened to reduce the removal rate.
Comparative example 6
Firstly, preparing water with the temperature of 50 ℃, adding carboxymethyl cellulose according to the mass ratio of the water to the carboxymethyl cellulose of 5:1, continuously stirring at the stirring speed of 200rpm until the carboxymethyl cellulose is completely dissolved to obtain a carboxymethyl cellulose solution; dispersing the nano zero-valent iron powder, then adding the dispersed nano zero-valent iron suspension into a carboxymethyl cellulose solution, and uniformly stirring at a stirring speed of 200rpm to obtain a mixed solution; the nano zero-valent iron and the carboxymethyl cellulose are added according to the mass ratio of 10:2.
And after stirring, quickly carrying out solid-liquid separation on the solution to obtain the iron-based nano material, wherein the water content is 50%, and hermetically packaging the iron-based nano material to prevent the material from being oxidized and losing efficacy.
The experimental methods and the amounts of materials added were as above, and the results are shown in Table 2.
TABLE 2 results of removing heavy metal contaminated groundwater
| Zinc (mg/L) | Lead (mg/L) | Arsenic (mg/L) | |
| Raw Water composition | 1.8 | 0.15 | 0.69 |
| Comparative example 6 | 1.2 | 0.14 | 0.41 |
Comparative example 7
And dispersing the nano zero-valent iron powder to obtain the nano zero-valent iron suspension. Then slowly adding activated carbon powder into the dispersed nano zero-valent iron suspension, and continuously stirring and uniformly mixing. The nano zero-valent iron and the activated carbon are added according to the mass ratio of 10: 5.
And after stirring is finished, rapidly carrying out solid-liquid separation on the solution to obtain the iron-based nano material, wherein the water content is 50%, and hermetically packaging to prevent the material from being oxidized and losing efficacy.
The experimental methods and the amounts of materials added were the same as above, and the effects of use are shown in table 3.
TABLE 3 results of removing heavy metal contaminated groundwater
| Zinc (mg/L) | Lead (mg/L) | Arsenic (mg/L) | |
| Raw Water composition | 1.8 | 0.15 | 0.69 |
| Comparative example 7 | 0.9 | 0.13 | 0.37 |
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The iron-based nano material for in-situ remediation of heavy metal polluted underground water is characterized by being prepared from nano zero-valent iron, nano ferroferric oxide, an oxidation inhibitor and activated carbon, wherein the mass ratio of the nano zero-valent iron to the nano ferroferric oxide to the oxidation inhibitor to the activated carbon is 10: 1.5-2.5: 3-7.
2. The iron-based nanomaterial of claim 1, wherein the oxidation inhibitor comprises one or more of carboxymethyl cellulose, chitosan, and soluble starch.
3. The method for preparing an iron-based nanomaterial of claim 1 or 2, comprising the steps of:
1) dissolving the oxidation inhibitor in water to obtain an oxidation inhibitor solution;
2) dispersing the nano zero-valent iron to obtain a nano zero-valent iron suspension; dispersing the nano ferroferric oxide to obtain a nano ferroferric oxide suspension; mixing the nano zero-valent iron suspension, the nano ferroferric oxide suspension and the antioxidant solution obtained in the step 1) to obtain a mixed solution;
3) mixing the mixed suspension obtained in the step 2) with activated carbon, and carrying out solid-liquid separation to obtain a solid which is an iron-based nano material;
the mass ratio of the nano zero-valent iron to the nano ferroferric oxide to the antioxidant to the active carbon is 10: 1.5-2.5: 3-7.
4. The method according to claim 3, wherein the temperature of the water in the step 1) is 40 to 80 ℃.
5. The preparation method according to claim 3, wherein the mass ratio of the water in the step 1) to the oxidation inhibitor is 3-8: 1.
6. The method according to claim 5, wherein the mass ratio of the water to the oxidation inhibitor is 5: 1.
7. The preparation method according to claim 3, wherein the mixing in step 2) and step 3) is carried out under stirring at a speed of 100-300 rpm.
8. The use of the iron-based nanomaterial of claim 1 or 2 in situ remediation of heavy metal contaminated groundwater.
9. The application according to claim 8, wherein the application comprises: the total mass of the heavy metal in the groundwater is 1g/m 3 In the case of the iron-based nanomaterial, the addition amount of the iron-based nanomaterial is 10g/m 3 。
10. Use according to claim 8, wherein the heavy metal comprises one or more of zinc, lead and arsenic.
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