CN105195758A - Preparation method and application of nano zero-valence iron and copper double-metal particles - Google Patents
Preparation method and application of nano zero-valence iron and copper double-metal particles Download PDFInfo
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- CN105195758A CN105195758A CN201510534820.3A CN201510534820A CN105195758A CN 105195758 A CN105195758 A CN 105195758A CN 201510534820 A CN201510534820 A CN 201510534820A CN 105195758 A CN105195758 A CN 105195758A
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Abstract
The invention relates to a preparation method and application of nano zero-valence iron and copper double-metal particles. In one embodiment, the preparation method comprises the following steps: adding an iron salt and a copper salt into a three-opening flask at a mol ratio of (3-10) to 1; taking 50mL-100mL of an ethanol solution to be added into the three-opening flask; stirring in a water bath at 20 DEG C to 60 DEG C for 10 minutes to 30 minutes; adding a hydroborate solution into the three-opening flask; after stirring for 10 minutes to 40 minutes, filtering to obtain sediment; washing the sediment with absolute ethyl alcohol and acetone respectively and then filtering; and putting the sediment into a vacuum drying box to be dried for 1 hour to 24 hours at 25 DEG C to 80 DEG C to obtain the nano zero-valence iron and copper double-metal particles. According to the embodiment provided by the invention, a preparation process is simple and the utilization is safe; and by adjusting the pH of chromium polluted soil, the application amount of the nano zero-valence iron and copper double-metal particles and a reaction temperature, hexavalent chromium in the chromium polluted soil can be rapidly reduced, so that the embodiment has a great application value in the field of repairing the chromium polluted soil.
Description
Technical field
The present invention relates to metal nanoparticle technical field, particularly relate to a kind of Preparation method and use of nano zero-valence iron-copper bi-metal particle.
Background technology
Along with fast development that is industrial, agriculture and urbanization, problem of environmental pollution is on the rise, and wherein heavy metal pollution of soil problem is very outstanding.China is the big producing country of chromic salts in the world, and can produce a large amount of chromium slags in the process of chromium salt production, the Cr VI in chromium slag has carcinogenesis to human body, and strong toxicity is easily absorbed by the body, constantly can accumulate in human body.China discharges chromium slag about 600,000 tons every year, and the soil more than 1,250 ten thousand tons that China is subject to Cr VI severe contamination, chromium slag through rain-out under infilter into soil and groundwater and rainwash, cause serious soil Cr and pollute.
Nano zero valence iron is because its reducing power is strong, cost is low, and abrasive grit footpath is little, easily moves in water body, can flexible Application in the original position of superficial water, underground water and soil and showering.But nano zero valence iron poor stability, easily oxidized and corrosion occurs form passivation layer its surface-active is deteriorated in soil and groundwater, reduce chromic remediation efficiency, limit its application in practice.
The restorative procedure of prior art to chromium-polluted soil has microbial method, chemical method, Physical etc., but has that remediation efficiency is low, cost is high, secondary pollution and the large shortcoming of environmental risk.Therefore, the present invention proposes that a kind of stability is strong, reaction rate is fast, the Preparation method and use of the simple nano zero-valence iron base metallic particles of processing technology.
Summary of the invention
The object of the invention is the special construction for existing nano zero valence iron, cause nano zero valence iron particle easily to be reunited and in application process particle surface oxidizable make reaction rate reduce problem, a kind of ferric ion is proposed and bivalent cupric ion adds in ethanolic solution simultaneously, and add the method that reducing agent prepares nano zero-valence iron-copper bi-metal particle, and the purposes of nano zero-valence iron-copper bi-metal particle in chromium-polluted soil is repaired.
For achieving the above object, the invention provides a kind of Preparation method and use of nano zero-valence iron-copper bi-metal particle, preparation method comprises the following steps:
(1) be that 3 ~ 10:1 adds there-necked flask in molar ratio by molysite and mantoquita;
(2) ethanolic solution getting 50mL ~ 100mL adds there-necked flask, 20 DEG C ~ 60 DEG C stirring in water bath 10 ~ 30min;
(3) add in there-necked flask by borohydride salts solution, after stirring 10 ~ 40min, suction filtration is precipitated thing;
(4) by the sediment in step (3) respectively with suction filtration after absolute ethyl alcohol and acetone cleaning, put into dry 1h ~ 24h under vacuum drying chamber 25 DEG C ~ 80 DEG C conditions, obtain nano zero-valence iron-copper bi-metal particle;
Wherein, step (2)-(3) are carried out in a nitrogen atmosphere.
Preferably, molysite is one or more in iron chloride, ferric sulfate and ferric nitrate, and mantoquita is one or both in copper sulphate, copper chloride.
Preferably, the volumetric concentration of ethanolic solution is 50%-90%.
Preferably, in borohydride salts solution, solute is sodium borohydride or potassium borohydride.
Particularly, the mol ratio of sodium borohydride or potassium borohydride and molysite is 1 ~ 10:1.
The purposes of nano zero-valence iron-copper bi-metal particle, for the reparation of chromium-polluted soil.
Preferably, the reparation of chromium-polluted soil comprises the following steps: first regulate soil pH to 2 ~ 5, then add in soil by nano zero-valence iron-copper bi-metal particle; The use amount of nano zero-valence iron-copper bi-metal particle is not less than 18g/kg; Temperature is regulated to be not less than 20 DEG C.
The Preparation method and use of a kind of nano zero-valence iron-copper bi-metal of the present invention particle, this preparation method carries out reduction prepare by trivalent iron salt and cupric salt to be added in ethanolic solution simultaneously, and technique is simple, reagent is easy to obtain, the features such as cost is low.The purposes of nano zero-valence iron-copper bi-metal particle of the present invention, by regulating the pH of chromium-polluted soil, the applied amount of nano zero-valence iron-copper bi-metal particle and reaction temperature, can repair chromium-polluted soil in 30min, drastically increase chromic rate of reduction in chromium-polluted soil, avoid the oxidation of nano zero-valence iron-copper bi-metal particle in course of reaction, and the method reaction efficiency high, be easy to promote, low, the use safety of cost, avoid the secondary pollution caused in repair process, in reparation chromium-polluted soil field, there is huge using value.
Accompanying drawing explanation
The pH that Fig. 1 provides for the embodiment of the present invention is on the impact of hexavalent chromium removal rate;
The pH that Fig. 2 provides for the embodiment of the present invention is on the impact of hexavalent chromium removal speed;
The temperature that Fig. 3 provides for the embodiment of the present invention is on the impact of hexavalent chromium removal rate;
The temperature that Fig. 4 provides for the embodiment of the present invention is on the impact of hexavalent chromium removal speed;
The nano zero-valence iron-copper bi-metal particle applied amount that Fig. 5 provides for the embodiment of the present invention is on the impact of hexavalent chromium removal rate;
The nano zero-valence iron-copper bi-metal particle applied amount that Fig. 6 provides for the embodiment of the present invention is on the impact of hexavalent chromium removal speed.
Detailed description of the invention
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Embodiment 1
The preparation method of the nano zero-valence iron-copper bi-metal particle of the present embodiment, comprise the following steps: 3mmol ferric sulfate and 1mmol copper sulphate are added in there-necked flask, add the ethanolic solution of 50mL90% again, 60 DEG C of stirring in water bath 10min, then 24mL1mol/L sodium borohydride solution is added in there-necked flask, after stirring 25min, suction filtration is precipitated thing, and above operating procedure is carried out all in a nitrogen atmosphere.Gained sediment is drained with after absolute ethyl alcohol and acetone cleaning respectively, puts into dry 12h under vacuum drying chamber 60 DEG C of conditions, obtain nano zero-valence iron-copper bi-metal particle.
Embodiment 2
The preparation method of the nano zero-valence iron-copper bi-metal particle of the present embodiment, comprise the following steps: 7.2mmol iron chloride and 0.9mmol copper chloride are added in there-necked flask, add the ethanolic solution of 60mL80% again, 25 DEG C of stirring in water bath 30min, then 36mL1.2mol/L solution of potassium borohydride is added in there-necked flask, after stirring 20min, suction filtration is precipitated thing, and above operating procedure is carried out all in a nitrogen atmosphere.Gained sediment is drained with after absolute ethyl alcohol and acetone cleaning respectively, puts into dry 18h under vacuum drying chamber 70 DEG C of conditions, obtain nano zero-valence iron-copper bi-metal particle.
Embodiment 3
The preparation method of the nano zero-valence iron-copper bi-metal particle of the present embodiment, comprise the following steps: 2mmol ferric nitrate and 0.2mmol copper sulphate, 0.2mmol copper chloride are added in there-necked flask, add the ethanolic solution of 70mL70% again, 20 DEG C of stirring in water bath 25min; Then add 1mL2mol/L sodium borohydride solution in there-necked flask, after stirring 40min, suction filtration is precipitated thing, and above operating procedure is carried out all in a nitrogen atmosphere.Gained sediment is drained with after absolute ethyl alcohol and acetone cleaning respectively, puts into dry 16h under vacuum drying chamber 40 DEG C of conditions, obtain nano zero-valence iron-copper bi-metal particle.
Embodiment 4
The preparation method of the nano zero-valence iron-copper bi-metal particle of the present embodiment, comprise the following steps: 4mmol ferric sulfate, 8mmol iron chloride and 1.2mmol copper sulphate are added in there-necked flask, add the ethanolic solution of 80mL60% again, 40 DEG C of stirring in water bath 20min, then 40mL3mol/L solution of potassium borohydride is added in there-necked flask, after stirring 40min, suction filtration is precipitated thing, and above operating procedure is carried out all in a nitrogen atmosphere.Gained sediment is drained with after absolute ethyl alcohol and acetone cleaning respectively, puts into dry 1h under vacuum drying chamber 25 DEG C of conditions, obtain nano zero-valence iron-copper bi-metal particle.
Embodiment 5
The preparation method of the nano zero-valence iron-copper bi-metal particle of the present embodiment, comprise the following steps: 10mmol iron chloride, 4mmol ferric sulfate, 4mmol ferric nitrate and 2mmol copper chloride are added in there-necked flask, add the ethanolic solution of 100mL50% again, 30 DEG C of stirring in water bath 15min; Then add 48mL1.5mol/L sodium borohydride solution in there-necked flask, after stirring 10min, suction filtration is precipitated thing, and above operating procedure is carried out all in a nitrogen atmosphere.Gained sediment is drained with after absolute ethyl alcohol and acetone cleaning respectively, puts into dry 24h under vacuum drying chamber 80 DEG C of conditions, obtain nano zero-valence iron-copper bi-metal particle.
Embodiment 6
The purposes of the present embodiment 1 nano zero-valence iron-copper bi-metal particle, carries out according to following steps: get the chromyl contaminated soil of 5g and 50mL acetum fully mixes, and regulate pH of mixed to 4, vibrate 24h. at 35 DEG C, makes Cr VI stripping in soil.Nano zero-valence iron-copper bi-metal particle 0.095g obtained in embodiment 1 is added chromium-polluted soil mixed liquor, 50 DEG C of water-bath vibration 30min.Filter, record the Cr VI in solution by diphenyl phosphinylidyne two hydrazine method.
Embodiment 7
The purposes of the present embodiment 2 nano zero-valence iron-copper bi-metal particle, carries out according to following steps: get the chromyl contaminated soil of 5g and 50mL acetum fully mixes, and regulate pH of mixed to 5, vibrate 24h at 25 DEG C, makes Cr VI stripping in soil.Nano zero-valence iron-copper bi-metal particle 0.125g obtained in embodiment 2 is added chromium-polluted soil mixed liquor, 50 DEG C of water-bath vibration 30min.Filter, record the Cr VI in solution by diphenyl phosphinylidyne two hydrazine method.
Embodiment 8
The purposes of the present embodiment 3 nano zero-valence iron-copper bi-metal particle, carries out according to following steps: get the chromyl contaminated soil of 5g and 50mL acetum fully mixes, and regulate pH of mixed to 3, vibrate 24h at 30 DEG C, makes Cr VI stripping in soil.Nano zero-valence iron-copper bi-metal particle 0.115g obtained in embodiment 3 is added chromium-polluted soil mixed liquor, 50 DEG C of water-bath vibration 30min.Filter, record the Cr VI in solution by diphenyl phosphinylidyne two hydrazine method.
Embodiment 9
The purposes of the present embodiment 4 nano zero-valence iron-copper bi-metal particle, carries out according to following steps: get the chromyl contaminated soil of 5g and 50mL acetum fully mixes, and regulate pH of mixed to 5, vibrate 24h at 20 DEG C, makes Cr VI stripping in soil.Nano zero-valence iron-copper bi-metal particle 0.09g obtained in embodiment 4 is added chromium-polluted soil mixed liquor, 50 DEG C of water-bath vibration 30min.Filter, record the Cr VI in solution by diphenyl phosphinylidyne two hydrazine method.
Embodiment 10
The purposes of the present embodiment 5 nano zero-valence iron-copper bi-metal particle, carries out according to following steps: get the chromyl contaminated soil of 5g and 50mL acetum fully mixes, and regulate pH of mixed to 2, vibrate 24h at 20 DEG C, makes Cr VI stripping in soil.Nano zero-valence iron-copper bi-metal particle 0.1g obtained in embodiment 5 is added chromium-polluted soil mixed liquor, 50 DEG C of water-bath vibration 30min.Filter, record the Cr VI in solution by diphenyl phosphinylidyne two hydrazine method.
Table 1 embodiment 1-5 obtains product chromic clearance in chromium-polluted soil
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Existing product | |
| Clearance (%) | 96.9 | 95.74 | 98.84 | 95.26 | 98.02 | 90 |
The product that embodiment 1-5 obtains carries out chromic removal in chromic contaminated soil by the step of embodiment 6-10.As can be seen from Table 1, embodiment 1-5 obtains product and all reaches more than 95% to clearance chromic in chromium-polluted soil, higher than existing nano zero-valence iron product.
Nano zero-valence iron-copper bi-metal particle repairs chromium-polluted soil principle, and add nano zero-valence iron-copper bi-metal particle in soil after, in the soil liquid, nano zero-valence iron-copper bi-metal nano material can serve as a miniature galvanic cell, corrosion reaction can occur.In this galvanic cell, Fe is negative pole, and the oxidation reaction that Fe occurs generates ferrous ion; Cu is equivalent to positive pole, the H in the soil liquid
+be reduced generation evolving hydrogen reaction, the reaction that positive pole and negative pole occur is as follows:
Negative pole: Fe-2e → Fe
2+
Positive pole: 2H
++ 2e → H
2↑
Fe
0and Fe
2+all there is reproducibility, Fe
2+lose an electronics further and become Fe
3+, Cr
6+obtain electronics and become Cr
3+and be reduced.In the process of electro transfer, H
2be a kind of well electron donor, which carry electronics and by electro transfer to the Cr of nano zero-valence iron-copper bi-metal material surface
6+, make it be reduced to Cr
3+, along with the carrying out of reaction, H in the soil liquid
+concentration reduce, the pH of solution can increase gradually, Fe
3+and Cr
3+produce precipitation and be attached to nano zero-valence iron-copper bi-metal material surface, these beds of precipitation can adsorb and go back remaining Cr in native soil equally
6+.Cr in such soil
6+produced the absorption ~ reduction of precipitation by the absorption ~ reduction of nano zero-valence iron-copper bi-metal nano material and corrosion reaction, and reduce ~ be fixed on soil and nano zero-valence iron-copper bi-metal nano-material surface, reach and reduce Cr in soil
6+the object of concentration and toxicity.
Nano zero-valence iron-copper bi-metal material is to Cr in soil
6+reduction ~ fixing process in the chemical reaction that occurs as follows:
Cr
2O
7 2-+14H
++3Fe＝2Cr
3++3Fe
2++7H
2O
Cr
2O
7 2-+14H
++6Fe
2+＝2Cr
3++6Fe
3++7H
2O
Fe+CrO
4 2-+4H
2O＝Fe(OH)
3+Cr(OH)
3+2OH
-
xFe(OH)
3+(1-x)Cr(OH)
3＝(Fe
xCr
1-x)(OH)
3
Cu
2++2OH
-＝Cu(OH)
2
By the Cr in above-mentioned reaction soil
6+obtain reducing ~ fixing, reach and reduce Cr in soil
6+the object of concentration and toxicity.Redox products is (Fe
xcr
1 ~ x) (OH)
3, Cu (OH)
2deng, avoid the secondary pollution that in repair process, its redox products causes.
PH is on the impact of chromic treatment effeciency: get the hexavalent chromium polluted soil of 5g in conical flask, add the nano zero-valence iron-copper bi-metal particle of 0.01g, add 50mL acetum again, regulate pH value to 2 ~ 11 of mixed liquor, the 30min that vibrates in 25 DEG C of water-baths filters, and detects the chromic clearance in solution by diphenyl phosphinylidyne two hydrazine method.As shown in Figure 1, in the soil liquid, hexavalent chromium removal rate reduces along with the rising of soil liquid pH value, during soil liquid pH value <6, in soil, chromic clearance reaches more than 95%, when soil liquid pH value is 6, in soil, chromic clearance is sharply reduced to 28.13%, and when the pH value of the soil liquid is 11, nano zero-valence iron-copper bi-metal particle is reduced to 5.63% to clearance chromic in soil.As shown in Figure 2, soil liquid pH value is lower faster with chromic reaction rate in soil, and when soil liquid pH value is 2-5, in nano zero-valence iron-copper bi-metal particle and soil, Cr VI reacts 30min, and in soil, chromic clearance can reach more than 95%.
The applied amount of nano zero-valence iron-copper bi-metal particle is on the impact of chromic treatment effeciency: get the hexavalent chromium polluted soil of 5g in conical flask, add the nano zero-valence iron-copper bi-metal particle of different amount, add 50ml acetum again, regulate the pH value to 3 of mixed liquor, the 30min that vibrates in 25 DEG C of water-baths filters, and detects the chromic clearance in solution by diphenyl phosphinylidyne two hydrazine method.As shown in Figure 3, in the soil liquid, chromic clearance increases along with the rising of nano zero-valence iron-copper bi-metal particle dosage, when in the soil liquid, nano zero-valence iron-copper bi-metal particle dosage is 15g/kg, in the soil liquid, chromic clearance is below 40%, when in the soil liquid, nano zero-valence iron-copper bi-metal particle dosage is 17g/kg, in the soil liquid, hexavalent chromium removal rate reaches 89%, when in the soil liquid, nano zero-valence iron-copper bi-metal particle dosage is more than or equal to 18g/Kg, in the soil liquid, hexavalent chromium removal rate is greater than 99%.As shown in Figure 4, in the soil liquid, nano zero-valence iron-copper bi-metal particle dosage is more faster with chromic reaction rate in soil, when in the soil liquid, nano zero-valence iron-copper bi-metal particle dosage is more than or equal to 18g/Kg, in nano zero-valence iron-copper bi-metal particle and soil, Cr VI reacts 30min, and in soil, chromic clearance can reach more than 99%.
Temperature is on the impact of chromic treatment effeciency: get the hexavalent chromium polluted soil of 5g in conical flask, add the nano zero-valence iron-copper bi-metal particle of 0.01g, add 50mL acetum again, regulate the pH to 3 of mixed liquor, the 30min that vibrates in 25 DEG C of water-baths filters, and detects the chromic clearance in solution by diphenyl phosphinylidyne two hydrazine method.As shown in Figure 5, in the soil liquid, chromic clearance increases along with the rising of temperature, when the temperature of the soil liquid is more than or equal to 20 DEG C, in soil, chromic clearance reaches more than 99%, when the temperature of the soil liquid is 15 DEG C, in soil, chromic clearance is reduced to 87%, and when the temperature of the soil liquid is 0 DEG C, in soil, chromic clearance is reduced to 54%.As shown in Figure 6, soil liquid temperature is higher faster with chromic reaction rate in soil, when soil liquid temperature is more than or equal to 20 DEG C, in nano zero-valence iron-copper bi-metal particle and soil, Cr VI reacts 30min, and in soil, chromic clearance can reach more than 99%.
Above-described detailed description of the invention; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only the specific embodiment of the present invention; the protection domain be not intended to limit the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a preparation method for nano zero-valence iron-copper bi-metal particle, is characterized in that, described preparation method comprises the following steps:
(1) be that 3 ~ 10:1 adds there-necked flask in molar ratio by molysite and mantoquita;
(2) ethanolic solution getting 50mL ~ 100mL adds described there-necked flask, 20 DEG C ~ 60 DEG C stirring in water bath 10 ~ 30min;
(3) add in described there-necked flask by borohydride salts solution, after stirring 10 ~ 40min, suction filtration is precipitated thing;
(4) by the sediment in step (3) respectively with suction filtration after absolute ethyl alcohol and acetone cleaning, put into dry 1h ~ 24h under vacuum drying chamber 25 DEG C ~ 80 DEG C conditions, obtain nano zero-valence iron-copper bi-metal particle;
Wherein, step (2)-(3) are carried out in a nitrogen atmosphere.
2. preparation method according to claim 1, is characterized in that, described molysite is one or more in iron chloride, ferric sulfate and ferric nitrate, and described mantoquita is one or both in copper sulphate, copper chloride.
3. preparation method according to claim 1, it is characterized in that, the volumetric concentration of described ethanolic solution is 50%-90%.
4. preparation method according to claim 1, it is characterized in that, in described borohydride salts solution, solute is sodium borohydride or potassium borohydride.
5. borohydride salts solution according to claim 4, it is characterized in that, the mol ratio of described sodium borohydride or potassium borohydride and described molysite is 1 ~ 10:1.
6. a purposes for claim 1 nano zero-valence iron-copper bi-metal particle, is characterized in that, for the reparation of chromium-polluted soil.
7. according to the purposes of claim 6 nano zero-valence iron-copper bi-metal particle, it is characterized in that, the reparation of described chromium-polluted soil comprises the following steps: first regulate soil pH to 2 ~ 5, then add in soil by nano zero-valence iron-copper bi-metal particle; The use amount of described nano zero-valence iron-copper bi-metal particle is not less than 18g/kg; Temperature is regulated to be not less than 20 DEG C.
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| CN113499775A (en) * | 2021-07-29 | 2021-10-15 | 合肥学院 | Nano zero-valent copper-iron composite porous material and preparation method and application thereof |
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