CN117756259A - Method for cooperatively treating metal pollutants by nano zero-valent iron and hydrogen nano bubbles - Google Patents
Method for cooperatively treating metal pollutants by nano zero-valent iron and hydrogen nano bubbles Download PDFInfo
- Publication number
- CN117756259A CN117756259A CN202410039960.2A CN202410039960A CN117756259A CN 117756259 A CN117756259 A CN 117756259A CN 202410039960 A CN202410039960 A CN 202410039960A CN 117756259 A CN117756259 A CN 117756259A
- Authority
- CN
- China
- Prior art keywords
- valent iron
- hydrogen
- nano
- bubbles
- zero
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000001257 hydrogen Substances 0.000 title claims abstract description 62
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 62
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002101 nanobubble Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 25
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002245 particle Substances 0.000 claims abstract description 36
- 239000003673 groundwater Substances 0.000 claims abstract description 16
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 230000002195 synergetic effect Effects 0.000 claims abstract description 6
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000356 contaminant Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 238000005065 mining Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 10
- 239000010865 sewage Substances 0.000 abstract description 2
- 238000007872 degassing Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229960001471 sodium selenite Drugs 0.000 description 4
- 235000015921 sodium selenite Nutrition 0.000 description 4
- 239000011781 sodium selenite Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000005273 aeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000003988 headspace gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides a method for cooperatively treating metal pollutants by nano zero-valent iron and hydrogen nano bubbles, belonging to the technical field of sewage and groundwater treatment. Adding nano zero-valent iron particles into a polluted water body under the anoxic condition, and introducing hydrogen nano bubbles to remove metal pollutants in the polluted water body; the nanometer zero-valent iron has a particle size of 20-200nm, a spherical core-shell structure and a core of Fe 0 An outer layer wraps the iron oxide; the average particle diameter of the hydrogen nano bubbles is 100-300nm, and the number of the bubbles is 10 7 ‑10 8 And each mL. The invention can enhance the reducibility of the system and promote the capability of treating pollutants by using the synergistic effect of the nano zero-valent iron and the hydrogen nano bubbles in the anoxic groundwater environment. The preparation method is simple, easy to realize, free of other harmful substances, clean and safe, capable of rapidly participating in removing underground water metal pollutants, and high in removing efficiency.
Description
Technical Field
The invention relates to the technical field of sewage and groundwater treatment, in particular to a method for cooperatively treating metal pollutants by nano zero-valent iron and hydrogen nano bubbles.
Background
In increasingly complex and evolving water pollution control, hundreds of water treatment technologies have been implemented. Purification of water is mainly based on physical-chemical processes such as particle aggregation, contaminant mitigation, disinfection and chemical oxidation, adsorption or bioconversion. Among the treatment technologies, nano zero-valent iron is an attractive nano material, and has great potential in the field of environmental remediation due to the characteristics of environmental friendliness, large specific surface area, low cost and the like. However, nano zero-valent iron is extremely easy to settle in water body and is extremely easy to react with water to cause corrosion. It is therefore desirable to surface modify it or change the exogenous conditions to promote the contaminant removal efficiency of nano zero-valent iron.
The unique characteristics of nanobubble technology for water treatment have attracted considerable attention to producing fewer byproducts and achieving safer water treatment. Nanobubbles are defined as bubbles with diameters less than 1000nm, which have many excellent properties and thus find wide application in water treatment: such as ultra-high stability, high mass transfer efficiency, high Zeta potential, special biological effects, etc.
There are various methods of generating nanobubbles including chemical reaction, ultrasonic cavitation, cyclic pressure change, water-solvent mixing, nanofiltration membrane filtration, gas compression/decompression, electrolysis, fluid oscillation, vibration, electric field, etc. Among them, hydrogen nanobubbles are reported to have important applications in the treatment of metal contamination and can exist stably in water. According to Henry's law, the solubility of hydrogen in water is 0.8mM (1.6 mg/L, w/v) at normal temperature and pressure, while the nanobubble technique can increase the solubility of hydrogen to 2.0mg/L, and about 0.5% of bubbles are present even after 8 to 13 months of storage. The hydrogen nanobubble technology is gradually applied to the environmental fields such as pollutant removal.
The technology of combining the hydrogen nano bubbles and the nano zero-valent iron is obviously expected to improve the reducibility of the anoxic groundwater environment, promote the charge transfer of the nano zero-valent iron, improve the sedimentation state, cooperate with the nano zero-valent iron to participate in the processes of chemical adsorption and the like, is expected to reduce the capital cost and the use of chemicals, does not generate secondary pollution, and is cleaner and more efficient.
Disclosure of Invention
In order to develop a simple and effective technology for removing underground water metal pollutants, the invention provides a method for cooperatively treating metal pollutants by nano zero-valent iron and hydrogen nano bubbles. The invention can enhance the reducibility of the system and promote the capability of treating pollutants by using the synergistic effect of the nano zero-valent iron and the hydrogen nano bubbles in the anoxic groundwater environment.
The technical scheme of the invention is as follows:
a method for cooperatively treating metal pollutants by nano zero-valent iron and hydrogen nano bubbles comprises the steps of adding nano zero-valent iron particles into a polluted water body under an anoxic condition, and introducing the hydrogen nano bubbles to remove the metal pollutants in the polluted water body;
the nanometer zero-valent iron has a particle size of 20-200nm, a spherical core-shell structure and a core of Fe 0 An outer layer wraps the iron oxide;
the average particle diameter of the hydrogen nano bubbles is 100-300nm, and the number of the bubbles is 10 7 -10 8 And each mL.
Preferably, the mass-volume ratio of the nano zero-valent iron particles to the polluted water body is 0.5-1.0g/L.
Preferably, the time for the synergistic treatment of the nano zero-valent iron and the hydrogen nano bubbles to treat the metal pollutants is 1-60min.
Preferably, the nano zero-valent iron is prepared by adopting a sodium borohydride liquid phase reduction method.
More preferably, the sodium borohydride liquid phase reduction method comprises the following steps:
(1) Preparing ferric chloride FeCl with the same volume 3 Solution and sodium borohydride NaBH 4 Solutions in which NaBH is present 4 With FeCl 3 The molar concentration ratio of (2) is not less than 4:1;
(2) NaB is purged with nitrogenH 4 Slowly dripping FeCl into the solution at a speed of 2-10mL/min 3 Mechanically stirring and fully mixing the solution; the nitrogen condition is preferably purity>99.9％；
(3)NaBH 4 After the solution is added dropwise, the obtained nZVI is collected by vacuum filtration, repeatedly washed by a large amount of deionized water and absolute ethyl alcohol, and then stored in the absolute ethyl alcohol at the temperature of 4 ℃ for standby.
Preferably, the preparation method of the hydrogen nanobubbles includes, but is not limited to: a micro-nano bubble machine method, a pressurizing and depressurizing method, an electrolysis method or a micropore medium method.
Preferably, the reaction temperature for cooperatively treating the metal pollutants by nano zero-valent iron and hydrogen nano bubbles is 20-30 ℃, and the system pressure is 1atm.
The metal contaminants that may be treated by the methods of the present invention include at least one of Mn, cr, cu, as, se, cd, sb, pb; and is versatile for other contaminating substances with oxidizing properties.
The polluted water body which can be treated by the method comprises underground water and further comprises mining area underground water.
The invention can also treat water bodies containing metal pollutants in other environments.
The beneficial technical effects of the invention are as follows:
1. according to the invention, a certain amount of nano zero-valent iron particles are added into the polluted groundwater, and hydrogen nano bubbles are introduced, so that under the anoxic condition, the bubbles improve the reducibility of a groundwater system, and the capability of removing metal pollutants by the nano zero-valent iron is enhanced. Since the hydrogen nanobubble has strong reducibility, its existence promotes Fe in addition to Fe 0 Besides the chemical reduction of (a), the removal of pollutants in the anaerobic polluted water body is promoted.
2. The invention only needs a certain amount of nano zero-valent iron particles and hydrogen nano bubbles, has simple preparation method, is easy to realize, has no other harmful substances, is clean and safe, can rapidly participate in the removal of underground water metal pollutants, and has high removal efficiency.
3. The invention can quickly participate in the removal of the groundwater pollutants in a short time without any catalyst, and has high removal efficiency. The technology of combining nano zero-valent iron and hydrogen nano bubbles is expected to improve the reducibility of the anoxic groundwater environment, the hydrogen nano bubbles cooperate with the nano zero-valent iron to participate in the processes of chemical adsorption and the like, capital cost and chemical use are expected to be reduced, sedimentation of the nano zero-valent iron is effectively avoided, and removal efficiency is improved.
4. The anaerobic environment and other environmental conditions required by the invention are just suitable for the anaerobic groundwater environment. The invention has no corrosive solution and no other harmful substances, accords with the environmental safety principle, and is suitable for treating groundwater.
Drawings
FIG. 1 is an experimental flow chart of the present invention for treating a contaminated water body.
Fig. 2 is the physical properties and stability of the hydrogen nanobubbles prepared in example 1, wherein: (a) The corresponding relation between the hydrogen nano bubble number density and the hydrogen content (the embedded graph is a dynamic light scattering light spot graph of each system respectively); (b) particle size distribution of hydrogen nanobubbles; (c) average particle diameter of hydrogen nanobubbles.
FIG. 3 is a graph showing the time-dependent removal rate of As in example 3.
Fig. 4 is a graph showing the change with time of Se removal rate in example 4.
FIG. 5 is a graph showing the concentration of Fe ions with time in example 4.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The chemical reagents used in the examples below include FeCl 3 ·6H 2 O、NaBH 4 And Na (Na) 2 SeO 3 (AR, sigma Aldrich (Shanghai) trade Co., ltd.). Deionized water was prepared by the ultrapure water system (Smart, health Force biomedical sciences, inc.). High purity nitrogen (pure)The degree is more than or equal to 99.9 percent) is used for deoxidizing the solution and is used as vacuum protective gas of various characterization instruments. The Particle size and Particle number density of the hydrogen nanobubbles were determined by a nanoparticle tracking analyzer (NTA, zetaView, particle metric, germany).
To prevent oxidation of the nanoscale zero-valent iron, the iron is generally stored in an ethanol solution at 4 ℃. Before adding the nano zero-valent iron, the nano zero-valent iron ethanol suspension is subjected to ice bath ultrasonic treatment for 30min to better disperse the agglomerated particles. The actual particle concentration of the nano zero-valent iron ethanol suspension is measured by a constant weight method.
Because of the extremely low solubility of hydrogen in water, the invention requires a certain anoxic or anaerobic environment in order for the hydrogen nanobubbles to be generated effectively and exist stably.
The reaction system of the following example is placed in a constant temperature shaking table in the whole course, the temperature is 25 ℃, the rotation speed is 180 r/min, the solution is completely and uniformly mixed, the full reaction is obtained, and the operation of the instrument is shown in figure 1.
Example 1: preparation and determination of Hydrogen nanobubble Water Performance
High purity hydrogen (H) was obtained by using micro-nano bubble device (OxYDEEP-TABLE-0.3, nanjing Bona scientific instruments Co., ltd.) 2 And (2) introducing 99.999% or more and Wen Dong (Shanghai) chemical products sales limited company) into the ultrapure water, wherein the rotation speed of the pump is 2300r/min, the gas flow is 100mL/min, the pump outlet pressure is 0.5MPa, and the running time of the instrument is 30min.
The solution is milky white in the running process because the water contains a large number of microbubbles, which are not visible to the naked eye. After the operation is finished, standing is carried out for 1min, the micro bubbles gradually disappear from bottom to top, and the solution is changed from milky white to clear and transparent.
The number density and particle size distribution of bubbles in the prepared hydrogen nanobubble water were measured by a nanoparticle tracking analyzer (25 ℃ C., sensitivity:65, shitter: 150). The total hydrogen content of the solution was determined by headspace gas chromatography. After deep degassing (after complete freezing at-20 ℃ C. And degassing at 0.1 atm for 10 hours, freezing again to eliminate the bubble particles in the solution), the concentration of the sample was again determined, and the deep degassing allowed for the removal of most of the gases in the system, including the dissolved gases and the nanobubble-encapsulated gases, and the changes in the concentration of the sample particles before and after degassing were compared. The test results are shown in fig. 2.
It can be seen from FIG. 2a that 3 deaerations can result in a particle number density of 3.8X10 in the hydrogen nanobubble water 8 The volume per mL is reduced to 6.7X10 6 Each mL is close to the number density of particles in ultra pure water (1.5-5.5X10) 6 and/mL). A small amount of hydrogen was detected in the solution after 2 times of deaeration, and 3 times of deaeration can completely remove hydrogen in the water body. The hydrogen nano-bubbles prepared by the equipment are stable in water, and at least 3 times of freezing-vacuum degassing are needed to completely remove the hydrogen nano-bubbles in the solution. The dynamic light scattering spot of the nanobubbles in solution measured by the nanoparticle tracking analyzer is shown in the inset of fig. 2 a.
FIG. 2b shows that the nanoparticle size distribution in freshly prepared hydrogen nanobubble water is concentrated at 50-250nm, the particle size after degassing is also in this range but the particle count is significantly reduced, and the particle size distribution is more dispersed as the number of degassing increases.
The average particle size of the freshly prepared hydrogen nanobubbles was 144.6.+ -. 88.9nm, while the average particle size after deaeration was about 250nm, indicating that deaeration had a large influence on the hydrogen nanobubble water system, not only reducing the number of bubbles, but also increasing the bubble particle size. Therefore, the particle size and the number density of the hydrogen nanobubbles can be changed to a certain extent in the practical application process, but the change has little influence on the removal of metal pollutants.
Example 2: preparation of nano zero-valent iron
The nano zero-valent iron is prepared by adopting a sodium borohydride liquid phase reduction method, and comprises the following specific steps:
(1) Preparation of 0.05M ferric chloride (FeCl) 3 ) Solution and the same volume of 0.2M sodium borohydride (NaBH) 4 ) A solution;
(2) Under nitrogen (N) 2 Purity of>99.9%) of NaBH is purged 4 Slowly dripping FeCl into the solution at a speed of 2-10mL/min 3 Mechanically stirring and fully mixing the solution;
(3)NaBH 4 after the solution is added dropwise, the obtained nZVI is collected by vacuum filtration, repeatedly washed by a large amount of deionized water and absolute ethyl alcohol, and then stored in the absolute ethyl alcohol at the temperature of 4 ℃ for standby. Before use, the nanometer zero-valent iron ethanol suspension is subjected to ice bath ultrasonic treatment for 30min to prevent agglomeration.
The nano zero-valent iron prepared by the method is of a spherical core-shell structure, and the core is Fe 0 The outer layer is coated with iron oxide, and the particle size range is 20-200nm.
Example 3: nanometer zero-valent iron and hydrogen nanometer bubble synergistic treatment As 3+ Metal contamination
Preparing the alloy containing As 3+ 100mg/L sodium selenite solution is put in a triangular flask, 1.0g/L nanometer zero-valent iron ethanol suspension is added after pH=5.00 is regulated, and the triangular flask is oscillated for 2 hours at 25 ℃ in a constant temperature shaking table after being quickly sealed by a rubber plug.
Preparing the alloy containing As 3+ The solvent used in the sodium selenite solution was hydrogen nanobubble water in example 1 without degassing, which was called the experimental group; the control group adopts deionized water as a solvent, and high-purity nitrogen is used for aeration deoxygenation of the deionized water in advance to simulate the anoxic groundwater environment, and then deep degassing is carried out to eliminate system bubble particles.
Sampling in segments according to reaction time of 0, 1, 5, 10, 15, 20, 30, 45, 60, 90, 120min, filtering with 0.22 μm filter membrane, 4% ultra-high purity HNO 3 The deionized water is acidified to a volume of 10mL. The soluble total As ions were measured using inductively coupled plasma (ICP, agilent 720ES, USA) (FIG. 3).
As can be seen from FIG. 3, compared with the control group, the removal rate of As ions can be obviously improved in the presence of the hydrogen nanobubbles, and the removal is basically completed after 10 min. This suggests that the presence of hydrogen nanobubbles accelerates the removal of As early in the reaction.
Example 4: synergistic Se treatment by nano zero-valent iron and hydrogen nano bubbles 4+ Metal contamination
Preparing Se-containing alloy 4+ 100mg/L sodium selenite solution is put into a triangular flask, and 1.0g/L nano zero-valent iron ethanol suspension is added after the pH value is regulated to be 5.00The turbid liquid is rapidly sealed by a rubber plug, and then the triangular flask is oscillated for 2 hours at 25 ℃ in a constant temperature shaking table.
Preparing Se-containing alloy 4+ The solvent adopts the prepared hydrogen nano bubble water when the sodium selenite solution is called an experimental group; the control group adopts deionized water as a solvent, and high-purity nitrogen is used for aeration deoxygenation of the deionized water in advance to simulate the anoxic groundwater environment, and then deep degassing is carried out to eliminate system bubble particles.
Sampling in segments according to reaction time of 0, 1, 5, 10, 15, 20, 30, 45, 60, 90, 120min, filtering with 0.22 μm filter membrane, 4% ultra-high purity HNO 3 The deionized water is acidified to a volume of 10mL. The soluble total Se ions were measured using inductively coupled plasma (ICP, agilent 720es, usa) (fig. 4).
As can be seen from fig. 4, compared with the control group, the presence of the hydrogen nanobubbles can significantly improve the removal rate of Se ions, and can completely remove Se in the solution within 10min, which is consistent with the effect in example 2, and shows that the hydrogen nanobubbles have the same promotion effect on removing Se from nano zero-valent iron As in the As system.
Fig. 5 shows the concentration of Fe ions over time during the experiment. As can be seen from fig. 5, the presence of the hydrogen nanobubbles slows down the precipitation rate of Fe ions and also reduces the concentration of Fe ions in the solution. The hydrogen nano bubbles have stronger reduction characteristic and can reduce free Fe ions into Fe 0 And participate in the reaction again, and the characteristic is highly matched with the anaerobic groundwater environment.
The experiment shows that the technology can effectively remove metal pollutants in underground water and has universality on other pollutants with oxidation property.
Although the embodiments of the present invention have been disclosed in the foregoing description and drawings, it is not limited to the details of the embodiments and examples, but is to be applied to all the fields of application of the present invention, it will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (10)
1. A method for cooperatively treating metal pollutants by nano zero-valent iron and hydrogen nano bubbles is characterized in that nano zero-valent iron particles are added into polluted water under the anoxic condition, and hydrogen nano bubbles are introduced to remove the metal pollutants in the polluted water;
the nanometer zero-valent iron has a particle size of 20-200nm, a spherical core-shell structure and a core of Fe 0 An outer layer wraps the iron oxide;
the average particle diameter of the hydrogen nano bubbles is 100-300nm, and the number of the bubbles is 10 7 -10 8 And each mL.
2. The method of claim 1, wherein the mass to volume ratio of the nano zero-valent iron particles to the contaminated water body is 0.5-1.0g/L.
3. The method of claim 1, wherein the time for the nanozero-valent iron and hydrogen nanobubbles to cooperatively treat the metal contaminants is 1-60 minutes.
4. The method of claim 1, wherein the nano zero-valent iron is prepared by a sodium borohydride liquid phase reduction method.
5. The method according to claim 4, wherein the sodium borohydride liquid phase reduction method comprises the steps of:
(1) Preparing ferric chloride FeCl with the same volume 3 Solution and sodium borohydride NaBH 4 Solutions in which NaBH is present 4 With FeCl 3 The molar concentration ratio of (2) is not less than 4:1;
(2) Under the condition of nitrogen purging, naBH is added 4 Slowly dripping FeCl into the solution at a speed of 2-10mL/min 3 Mechanically stirring and fully mixing the solution;
(3)NaBH 4 after the solution is added dropwise, the obtained nZVI is collected by vacuum filtration, repeatedly washed by a large amount of deionized water and absolute ethyl alcohol, and then stored in the absolute ethyl alcohol at the temperature of 4 ℃ for standby.
6. The method according to claim 1, wherein the preparation method of the hydrogen nanobubbles includes, but is not limited to: a micro-nano bubble machine method, a pressurizing and depressurizing method, an electrolysis method or a micropore medium method.
7. The method according to claim 1, wherein the reaction temperature for the synergistic treatment of metal contaminants with nanozero-valent iron and hydrogen nanobubbles is 20-30 ℃ and the system pressure is 1atm.
8. The method of claim 1, wherein the metal contaminants comprise at least one of Mn, cr, cu, as, se, cd, sb, pb.
9. The method of claim 1, wherein the contaminated body of water comprises groundwater.
10. The method of claim 1, wherein the contaminated water body comprises mining area groundwater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410039960.2A CN117756259A (en) | 2024-01-11 | 2024-01-11 | Method for cooperatively treating metal pollutants by nano zero-valent iron and hydrogen nano bubbles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410039960.2A CN117756259A (en) | 2024-01-11 | 2024-01-11 | Method for cooperatively treating metal pollutants by nano zero-valent iron and hydrogen nano bubbles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117756259A true CN117756259A (en) | 2024-03-26 |
Family
ID=90310828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410039960.2A Pending CN117756259A (en) | 2024-01-11 | 2024-01-11 | Method for cooperatively treating metal pollutants by nano zero-valent iron and hydrogen nano bubbles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117756259A (en) |
-
2024
- 2024-01-11 CN CN202410039960.2A patent/CN117756259A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kyzas et al. | Nanobubbles effect on heavy metal ions adsorption by activated carbon | |
| Wu et al. | Role of bulk nanobubbles in removing organic pollutants in wastewater treatment | |
| CN104710052B (en) | Method and device for treating high-concentration nitrobenzene-containing waste water by using air-stripping-microelectrolysis-fenton oxidation method | |
| CN102674641B (en) | Ultraviolet light ozone reaction process and device | |
| CN110272112B (en) | Colloidal ozone bubbles and preparation method and application thereof | |
| WO2013123780A1 (en) | Advanced treatment method for biochemical tail water of coking wastewater | |
| CN110369151B (en) | Method for treating heavy metal wastewater by nano collector ion flotation | |
| Corpuz et al. | Enhanced removal of mixed metal ions from aqueous solutions using flotation by colloidal gas aphrons stabilized with sodium alginate | |
| CN108392961B (en) | Nano-bubble organic waste gas treatment method and system | |
| Liao et al. | Rational assembly of GO-based heterocyclic sulfur-and nitrogen-containing aerogels and their adsorption properties toward rare earth elementals | |
| Bui et al. | Decolorization of dark green Rit dye using positively charged nanobubbles technologies | |
| CN104445741A (en) | Treatment method of oilfield ASP flooding produced sewage | |
| CN106977023A (en) | A kind of processing method of mechanical processing industry cutting waste fluid | |
| Yamini et al. | Ultra efficient removal of Basic Blue 41 from textile industry’s wastewaters by sodium dodecyl sulphate coated magnetite nanoparticles: Removal, kinetic and isotherm study | |
| CN114031167B (en) | Method for synchronously removing microplastic and quinolone antibiotics in water | |
| CN114804499A (en) | Oil-containing seawater treatment process | |
| CN102744030B (en) | Graphite oxide-containing nano-material, its preparation method, water treatment agent and its water treatment method | |
| Bogacki et al. | Automotive fleet repair facility wastewater treatment using air/ZVI and air/ZVI/H2O2 processes | |
| CN117756259A (en) | Method for cooperatively treating metal pollutants by nano zero-valent iron and hydrogen nano bubbles | |
| CN107226554A (en) | A kind of method of ferrous salt activation persulfate pretreatment Ghana filter point salt treatment RO/NF concentrated waters | |
| Singh et al. | Advancing nanobubble technology for carbon-neutral water treatment and enhanced environmental sustainability | |
| Wang et al. | Generation of reactive oxygen species from oxygen microbubbles in phosphoric acid solution and its application of ferrous iron oxidation | |
| Zhang et al. | Preparation of macroporous magnetic particles for the treatment of wastewater containing emulsified oil | |
| CN112520841A (en) | Polyurethane sponge biological filler and preparation method thereof | |
| JP3965118B2 (en) | Remediation of contaminated ground by injection of reactants |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |