CN110357240B - Water treatment method for reducing nitrosodimethylamine in water by cooperation of green rust and zero-valent iron - Google Patents
Water treatment method for reducing nitrosodimethylamine in water by cooperation of green rust and zero-valent iron Download PDFInfo
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- CN110357240B CN110357240B CN201910675912.1A CN201910675912A CN110357240B CN 110357240 B CN110357240 B CN 110357240B CN 201910675912 A CN201910675912 A CN 201910675912A CN 110357240 B CN110357240 B CN 110357240B
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- UMFJAHHVKNCGLG-UHFFFAOYSA-N n-Nitrosodimethylamine Chemical compound CN(C)N=O UMFJAHHVKNCGLG-UHFFFAOYSA-N 0.000 title claims abstract description 75
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000004458 analytical method Methods 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 238000005070 sampling Methods 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 241001311547 Patina Species 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000001963 growth medium Substances 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- -1 hydroxyl radicals Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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Classifications
-
- 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
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Removal Of Specific Substances (AREA)
Abstract
A water treatment method for reducing nitrosodimethylamine in water by cooperation of green rust and zero-valent iron, comprising the following steps: 1) preparing deionized oxygen-free water with set volume, wherein the initial pH value is 7.0; then 10 g.L of the mixture is added‑1The iron powder is added with 2.5-15 g.L respectively‑1Adding 100. mu.g.L of green rust‑1NDMA, covering the bottle cap tightly, and putting the bottle cap into a rotary incubator to rotate in a dark place; 2) and (3) sampling at regular time, performing filter pressing separation on the unreacted iron powder and the green rust of the sampled product by using a needle cylinder through a filter membrane of 0.22-0.45 mu m so as to terminate the reaction, and using the obtained water sample for the analysis and test of the NDMA concentration. The invention improves the degradation rate of NDMA.
Description
Technical Field
The invention belongs to the field of feedwater treatment, and relates to a chemical method for metal synergistic reduction.
Background
Nitrosodimethylamine (NDMA) is a substance with a high carcinogenic risk, and NDMA is classified as a class 2A carcinogen in the list of carcinogens published by the international cancer research institute of the world health organization. NDMA is present in many industrial processes such as leather making, rubber and tire manufacturing, pesticide and dye production, detergent and surfactant manufacturing, fish processing, casting, etc. NDMA was detected in water sources and subsequently discovered to be a disinfection by-product in the disinfection process in drinking and sewage treatment plants. The widespread presence of NDMA in water has raised high interest in the field of water treatment, and it is therefore necessary to develop techniques for its effective control.
Because NDMA has high solubility, low volatility, small octanol/water partition coefficient, small molecules, and no charge, it cannot be effectively treated by common treatment means (e.g., natural volatilization, gas stripping, soil and activated carbon adsorption, reverse osmosis). The existing strengthening treatment technology mainly comprises a biological method, membrane interception, adsorption, ozone oxidation, ultraviolet photolysis and a zero-valent iron reduction method. The long half-life of biological methods limits their use. Reverse osmosis membranes and nanofiltration membranes have no complete rejection. Hydrophobic adsorption materials do not effectively adsorb NDMA. Ozone cannot react directly with NDMA and its reaction with hydroxyl radicals generated in combination with hydrogen peroxide or uv is limited by free radical inhibitors in water. UV photolysis can effectively degrade NDMA, but requires a 10-fold UV dose of the normal disinfection process, about 1000 mJ-cm-2And the energy consumption is higher.
Disclosure of Invention
In order to overcome the defects of slow NDMA degradation speed and high energy consumption in the prior art, the invention provides a water treatment method for reducing nitrosodimethylamine in water by cooperation of patina (GR) and zero-valent iron, which can improve the NDMA degradation rate.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a water treatment method for reducing nitrosodimethylamine in water by cooperation of green rust and zero-valent iron, comprising the following steps:
1) preparing deionized oxygen-free water with set volume, wherein the initial pH value is 7.0; then 10 g.L of the mixture is added-1The iron powder is added with 2.5-15 g.L respectively-1Adding 100. mu.g.L of green rust-1NDMA, covering the bottle cap tightly, and putting the bottle cap into a rotary incubator to rotate in a dark place;
2) and (3) sampling at regular time, performing filter pressing separation on the unreacted iron powder and the green rust of the sampled product by using a needle cylinder through a filter membrane of 0.22-0.45 mu m so as to terminate the reaction, and using the obtained water sample for the analysis and test of the NDMA concentration.
Further, in the step 1), the culture medium is put into a rotary incubator QB-328 for 45 r.min-1The rotating speed of the rotating shaft is rotated in a dark place.
Further, in the step 2), the reaction time is 168-180 h.
The technical conception of the invention is as follows: in order to be applied to actual water treatment, a new simple and feasible treatment method capable of effectively removing the NDMA in the water needs to be established. The zero-valent iron reduction technology has wide raw material sources, low price and easy material obtaining, is applied to removing NDMA, but has longer reaction time and low removal rate when the NDMA is reduced by the zero-valent iron, and can become a novel simple and easy water treatment technology if a substance can be found to promote the reduction of the zero-valent iron so as to effectively degrade the NDMA. The patina is an oxidation product of iron, the structure of the patina has ferrous iron, the patina has certain reducing capability, but the reducing capability of the patina is lower than that of zero-valent iron, and the patina and the zero-valent iron are combined to form a potential difference, so that the rate of giving electrons out by the zero-valent iron is accelerated, and the degradation rate of the patina on NDMA is improved.
The invention has the following beneficial effects: the zero-valent iron powder can effectively remove NDMA existing in water under the cooperation of the green rust.
Drawings
FIG. 1 is a graph showing the comparison of the potency of Rust in combination with the reduction of NDMA [ NDMA]＝100μg·L-1pH 7.0 and rotation speed 45r min-1T20 ℃, wherein (a) represents Fe 10g/L and GR 2.5 g/L; (b) represents Fe is 10g/L, GR is 5 g/L; (c) represents Fe is 10g/L, GR is 10 g/L; (d) the formula is 10g/L for Fe and 15g/L for GR.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Referring to fig. 1, a water treatment method for reducing nitrosodimethylamine in water by cooperation of green rust and zero-valent iron comprises the following steps:
1) 8mL (set volume of 8mL) of deionized, oxygen-free water was added to an 8mL extraction flask at an initial pH of 7.0, followed by 10 g.L-1Respectively adding 2.5 g.L of the iron powder-1，5g·L-1，10g·L-1，15g·L-1Adding 100. mu.g.L of green rust-1NDMA, cover the bottle tightly, put into a rotary incubator QB-328 (manufactured by Nippon Linbel instruments Co., Ltd., Haimen) at 45 r.min-1The rotating speed of the rotating shaft is rotated in a dark place.
2) And (3) sampling at regular time, performing filter pressing separation on the unreacted iron powder and the green rust of the sampled product by using a needle cylinder through a filter membrane of 0.22-0.45 mu m so as to terminate the reaction, and using the obtained water sample for the analysis and test of the NDMA concentration. The reaction time is 168-180 h, and the removal rate of NDMA (ferric sulfate) by the cooperation of the green rust and the zero-valent iron cannot be obviously improved by continuously prolonging the reaction time.
FIG. 1 shows the respective ratios of 10 g.L-1Zero-valent iron powder of (2), 10 g.L-1Zero-valent iron powder and 2.5 g.L-1Mixture of patina, 10 g.L-1Zero-valent iron powder and 5 g.L-1Mixture of patina, 10 g.L-1Zero-valent iron powder and 10 g.L-1Mixture of patina, 10 g.L-1Zero-valent iron powder and 15 g.L-1The reduction initial concentration of the mixture of patina was 100. mu.g.L-1NDMA of (2).
As shown in FIGS. 1(a), (b), (c) and (d), the reaction is carried out for 168h, the removal rate of NDMA by zero-valent iron is 42%, while the removal rate of NDMA by green rust and zero-valent iron can reach 70% -90%, the reduction efficiency of the combination system to NDMA is improved along with the increase of the dosage of green rust, and after the reaction is carried out for 168h, 10 g.L-1Zero-valent iron powder and 15 g.L-1The removal rate of the mixed system of the patina to the NDMA can reach 89 percent, so that the patina can cooperate with the zero-valent iron to effectively reduce and degrade the NDMA compared with the zero-valent iron.
Claims (3)
1. A water treatment method for reducing nitrosodimethylamine in water by cooperation of green rust and zero-valent iron is characterized by comprising the following steps:
1) preparing deionized oxygen-free water with set volume, wherein the initial pH value is 7.0; then 10 g.L of the mixture is added-1The iron powder is added with 2.5-15 g.L respectively-1Adding 100. mu.g.L of green rust-1NDMA, covering the bottle cap tightly, and putting the bottle cap into a rotary incubator to rotate in a dark place;
2) and (3) sampling at regular time, performing filter pressing separation on the unreacted iron powder and the green rust of the sampled product by using a needle cylinder through a filter membrane of 0.22-0.45 mu m so as to terminate the reaction, and using the obtained water sample for the analysis and test of the NDMA concentration.
2. The method of claim 1, wherein the step 1) comprises placing the culture medium in a rotary incubator QB-328 for 45 r-min-1The rotating speed of the rotating shaft is rotated in a dark place.
3. The method for treating water by reducing nitrosodimethylamine in water by using patina in combination with zero-valent iron according to claim 1 or 2, wherein the reaction time in the step 2) is 168-180 h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2019104025848 | 2019-05-15 | ||
| CN201910402584 | 2019-05-15 |
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| CN110357240A CN110357240A (en) | 2019-10-22 |
| CN110357240B true CN110357240B (en) | 2022-05-03 |
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| CN111453875A (en) * | 2020-02-28 | 2020-07-28 | 浙江工业大学 | Water treatment method for N-nitrosodimethylamine in ferroferric oxide reinforced zero-valent iron reduction water |
| CN111977737A (en) * | 2020-07-30 | 2020-11-24 | 浙江工业大学 | Method for adsorbing tetracycline in underground water by using patina |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616913A (en) * | 2012-03-26 | 2012-08-01 | 同济大学 | Polyhydroxy ferrous complex reduction system, and preparation method and application thereof |
| CN105645551A (en) * | 2015-12-31 | 2016-06-08 | 浙江工业大学 | Treatment method for reducing nitrosodimethylamine in water by catalyzing zero-valent iron through copper corrosion product |
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| EP1740504B1 (en) * | 2004-04-26 | 2013-08-14 | Mitsubishi Materials Corporation | Method for producing reducing water purification material, method for treating wastewater, and wastewater treatment apparatus |
| US10640406B2 (en) * | 2016-05-17 | 2020-05-05 | Texas Tech University System | Surface modification of zero valent iron material for enhanced reactivity for degrading chlorinated contaminants in water |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616913A (en) * | 2012-03-26 | 2012-08-01 | 同济大学 | Polyhydroxy ferrous complex reduction system, and preparation method and application thereof |
| CN105645551A (en) * | 2015-12-31 | 2016-06-08 | 浙江工业大学 | Treatment method for reducing nitrosodimethylamine in water by catalyzing zero-valent iron through copper corrosion product |
Non-Patent Citations (1)
| Title |
|---|
| 绿锈还原转化邻氯硝基苯实验研究;吴德礼等;《同济大学学报（自然科学版）》;20101031;第38卷(第10期);第1473-1477页 * |
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