Patent Grant
12024446
The present invention belongs to the technical field of water treatment, and in particular to a magnetic powder strengthened method for removing nitrate nitrogen and inorganic phosphorus.
With the increasing population and accelerating processes of industrialization and urbanization, nitrogen in the natural water body has a trend toward a high level of nitration and can be transformed into substances such as nitrosamine in the water body, which threatens the ecological environment, animals and plants and human life and health. Therefore, World Health Organization, multiple countries and regions set pollution restriction indexes for nitrogen. As shown in reports or disclosures, nitrate nitrogen in the surface water, underground water, drinking water and wastewater around the world exceeds the standard quite seriously.
As for wastewater treatment, denitrification is the most common method for removing nitrate, which has a shortcoming that denitrifying bacteria need certain temperature and a biodegradable carbon source. Therefore, it is hard to popularize and apply denitrification in a large scale in a region with a relatively low temperature or for wastewater lacking a carbon source because raising the temperature or supplementing the carbon source will significantly increase the cost. Furthermore, the method is not applicable to the surface water, underground water or drinking water. Conventional physical and chemical methods mainly include reverse osmosis, ion exchange, reduction and the like, and each technique has respective advantages and shortcomings. Both the reverse osmosis and ion exchange are a separation method and do not eliminate nitrate fundamentally, but only separate pollutants through physical and chemical actions. Without further treatment, the pollutants are not yet disposed from a perspective of natural environment. Reduction with zero-valent iron and ferrous iron is an economical and efficient removal method which is widely studied and attracts much attention because of easiness in operation, a small floor area and a high reduction efficiency. Zero-valent iron, ferrous iron, green rust, Fe3O4 and the like all can be used as a reducing agent for nitrate nitrogen. However, it is quite difficult to control the reaction efficiency and reaction products of these reducing agents. In most actual cases, the reduction products are primarily ammonia nitrogen.
In the method for reduction treatment of nitrate in water disclosed by the patent (application No. 201310505699.2), reduction treatment is performed on nitrate by using the reducibility of green rust and the effects of catalyst ions, thus the nitrate is remarkably removed. But there still exists room for improvement in the removal of total nitrogen, and the removal of total phosphorus is not involved. The document (Environ. Sci. Technol., 2015, 49(24), 14401-14408) mentions that a magnetic field can generate convection in a solution to enhance transmission of substances, and can stimulate paramagnetic ions to migrate to increase the reaction rate. The method for treating sewage with a magnetic field disclosed by the patent (application No. 201510237845.7) presents that a magnetic field can effectively increase the removal rate of pollutants. However, since a general magnetic source acts in a small range and a small distance, it is hard to use the method in a large-scale reaction system in actual projects as the cost is added.
An objective of the present invention is to solve a problem that a magnetic field is hard to be evenly distributed in large-scale water treatment through the dispersion of hard magnetic powder based on the prior art, and to provide a magnetic field strengthened method for removing nitrate nitrogen and inorganic phosphorus, to realize efficient removal of nitrate nitrogen and total nitrogen, at the same time, remove inorganic phosphorus, simplify the process and lower the cost.
The technical solution of the present invention is as follows:
A magnetic powder strengthened method for removing nitrate nitrogen and inorganic phosphorus, comprising the following steps:
The present invention provides a water treatment method, in which a magnetic field is provided by a permanent magnetic material, a reducing agent is promoted to perform catalytic reduction on nitrate nitrogen to remove total nitrogen, and the product can be further combined with inorganic phosphorus (phosphate radical) for coagulating sedimentation to remove inorganic phosphorus. The removal rate of nitrate nitrogen by catalytic reduction and the degradation efficiency of total nitrogen in the to-be-treated water basically exceed 80%, and the removal rate of inorganic phosphorus in the to-be-treated water basically exceeds 90%. In some preferred solutions, the removal rate of nitrate nitrogen by catalytic reduction and the degradation efficiency of total nitrogen go beyond 90%.
In the method for removing nitrate nitrogen and inorganic phosphorus in water provided by the invention, in the step (1), the permanent magnetic material powder needs to be mixed with paramagnetic Fe3O4 so that a uniform and fine magnetic field can be provided near a catalytic reaction site after the permanent magnetic material powder is later added into the water treatment reaction vessel. The water treatment reaction vessel mentioned in the present invention may be a reactor or a reaction tank for water treatment.
In a solution, the concentration of the nitrate nitrogen in the to-be-treated water mentioned in the present invention is 40-500 mg/L. With the cooperation of other conditions, in a preferred solution, the concentration of the nitrate nitrogen in the to-be-treated water is 80-300 mg/L, and more preferably 200-250 mg/L.
In a preferred solution, in the step (3), before or after the to-be-treated water enters the water treatment reaction vessel, the reducing agent is added in batches or continuously. The to-be-treated water continuously enters the water treatment reaction vessel, in from one end and out from the other end, and a chemical reaction takes place in the flowing process. Or the to-be-treated water enters the water treatment reaction vessel and stays for a period of time to allow a chemical reaction to take place, and the water is discharged after the reaction is completed.
In a solution, the permanent magnetic material powder is one or more of a rare-earth permanent magnetic material, a metal permanent magnetic material or a ferrite permanent magnetic material. For example, without influencing the effect of the present invention, the rare-earth permanent magnetic material may be one or more of Sm—Co based, Nd—Fe—B, La—Ce or Re—Fe—B. The metal permanent magnetic material may be Al—Ni—Co, Fe—Cr—Co or a combination thereof. The ferrite permanent magnetic material may be one or more of α-Fe2O3, BaFe12O19 or SrFe12O19.
In a more preferred solution, in the step (1), a mass ratio of the permanent magnetic material powder to the paramagnetic Fe3O4 powder is 1:0.01-1:150. For example, without influencing the effect of the present invention, the mass ratio may be preferably 1:5-1:100, and in particular preferably 1:10-1:40.
In a preferred solution, an amount-of-substance ratio of the magnetic powder added in the step (2) to the nitrate nitrogen in the to-be-treated water in the step (3) is 1:0.01-1:100. Without influencing the effect of the present invention, the amount-of-substance ratio may be preferably 1:10-1:100, and more preferably 1:30-1:80.
In the present invention, the reducing agent added in the step (3) is a reducing substance, such as one or more of elemental zero-valent iron, elemental zero-valent aluminum, elemental zero-valent zinc, elemental zero-valent manganese, elemental zero-valent magnesium, a ferrous compound, a cuprous compound, green rust or Fe3O4, which can react with nitrate nitrogen and generates an oxidation product having a coagulation effect.
The ferrous compound mentioned in the present invention may be but not limit to ferrous chloride, ferrous sulfate and ferrous hydroxide.
The cuprous compound mentioned in the present invention may be but not limit to cuprous chloride, cuprous sulfate and cuprous hydroxide.
The green rust (GR) mentioned in the present invention may be but not limit to one or more of GR(SO42−), GR(CO32−), GR(Cl−) or GR(SO32−).
Further, in the step (3), the ratio of the dosage of the reducing agent to the amount of substance of the nitrate nitrogen in the to-be-treated water is 1:0.01-1:150; and without influencing the effect of the present invention, the ratio may be preferably 1:0.8-1:80, and more preferably 1:10-1:50.
In a preferred solution, a sludge discharge system may be disposed at the bottom of the water treatment reaction vessel mentioned in the step (2) of the present invention, to regularly clear the iron sludge generated by the removal of inorganic phosphorous.
In the step (3) of the present invention, the to-be-treated water entering the water treatment reaction vessel does not contain sodium hypochlorite, chloramine, ozone, sodium persulfate or potassium permanganate. Or a strong oxidant in the to-be-treated water is treated in advance, otherwise, the strong oxidant will react with the reducing agent to influence a reaction between the reducing agent and the nitrate nitrogen.
In a preferred solution, in the step (3), the reducing agent is added in batches or continuously, to ensure reduction of the nitrate nitrogen.
When the reducing agent is added in batches as mentioned in the present invention, each batch takes 5 min-1000 min, preferably 30 min-500 min.
The flow rate of the to-be-treated water continuously entering the water treatment reaction vessel as mentioned in the step (3) of the present invention is 0.1 L/h-1000 L/h.
After entering the water treatment reaction vessel as mentioned in the present invention, the time of the to-be-treated water staying in the water treatment reaction vessel is 1-600 minutes, preferably 1-300 minutes, and more preferably 1-50 minutes.
Further, in the step (3), stirring is mechanical stirring or hydraulic stirring.
The technical solution of the present invention has the following advantages:
(1) The magnetized permanent magnetic material powder provides a magnetic field and a uniform and fine magnetic field in the water treatment reaction vessel, thereby improving the reaction efficiency and facilitating the removal of nitrate nitrogen by catalytic reduction and the degradation of total nitrogen.
(2) Fe3O4 powder can serve as a catalyst to increase selectivity in the removal of total nitrogen, and the mixing of the magnetic powder and the reducing agent can enhance the stability of the reducing system.
(3) In the reaction process, the dissolved iron ions generated after the reaction of the iron-based reducing agent can serve as a coagulant to further remove inorganic phosphorus in the to-be-treated water, to realize removal of nitrogen and phosphorus.
(4) The whole catalytic reduction reaction is finished in a reaction system, in which water goes in from one end of the system and out from the other end, and the floor area is small. Moreover, through regular water cutoff and addition of the reducing agent, the activity of the reducing system can be restored, thus the reaction system is recycled, and the cost is saved.
The magnetic powder strengthened method for removing nitrate nitrogen and inorganic phosphorus of the present invention is further described with the following embodiments and in conjunction with drawings, but these embodiments do not constitute any limitation on the present invention.
As shown in
A magnetic powder strengthened method for removing nitrate nitrogen and inorganic phosphorus, including the following steps:
After the operation of the device, the concentration of the nitrate nitrogen in the to-be-treated water was 40 mg/L, and 14 mg/L in the yielding water, while the concentration of the total phosphorus in the to-be-treated water was 3 mg/L, and 0.4 mg/L in the yielding water.
A magnetic powder strengthened method for removing nitrate nitrogen and inorganic phosphorus, including the following steps:
After the operation of the device, the concentration of the nitrate nitrogen in the to-be-treated water was 80 mg/L, and 12 mg/L in the yielding water, while the concentration of total phosphorus in the to-be-treated water was 3 mg/L, and 0.2 mg/L in the yielding water.
A magnetic powder strengthened method for removing nitrate nitrogen and inorganic phosphorus, including the following steps:
After the operation of the device, the concentration of the nitrate nitrogen in the to-be-treated water was 50 mg/L, and 4 mg/L in the yielding water, while the concentration of the total phosphorus in the to-be-treated water was 5 mg/L, and 0.1 mg/L in the yielding water.
A magnetic powder strengthened method for removing nitrate nitrogen and inorganic phosphorus, including the following steps:
After the operation of the device, the concentration of the nitrate nitrogen in the to-be-treated water was 100 mg/L, and 11 mg/L in the yielding water, while the concentration of the total phosphorus in the to-be-treated water was 8 mg/L, and 0.4 mg/L in the yielding water.
A magnetic powder strengthened method for removing nitrate nitrogen and inorganic phosphorus, including the following steps:
After the operation of the device, the concentration of the nitrate nitrogen in the to-be-treated water was 60 mg/L, and 4 mg/L in the yielding water, while the concentration of the total phosphorus in the to-be-treated water was 9 mg/L, and 0.3 mg/L in the yielding water.
A magnetic powder strengthened method for removing nitrate nitrogen and inorganic phosphorus, including the following steps:
After the operation of the device, the concentration of the nitrate nitrogen in the to-be-treated water was 200 mg/L, and 13 mg/L in the yielding water, while the concentration of the total phosphorus in the to-be-treated water was 15 mg/L, and 0.2 mg/L in the yielding water.
A magnetic powder strengthened method for removing nitrate nitrogen and inorganic phosphorus, including the following steps:
After the operation of the device, the concentration of the nitrate nitrogen in the to-be-treated water was 80 mg/L, and 7 mg/L in the yielding water, while the concentration of the total phosphorus in the to-be-treated water was 20 mg/L, and 0.4 mg/L in the yielding water.
A magnetic powder strengthened method for removing nitrate nitrogen and inorganic phosphorus, including the following steps:
After the operation of the device, the concentration of the nitrate nitrogen in the to-be-treated water was 120 mg/L, and 13 mg/L in the yielding water, while the concentration of the total phosphorus in the to-be-treated water was 8 mg/L, and 0.2 mg/L in the yielding water.
A magnetic powder strengthened method for removing nitrate nitrogen and inorganic phosphorus, including the following steps:
After the operation of the device, the concentration of the nitrate nitrogen in the to-be-treated water was 250 mg/L, and 14 mg/L in the yielding water, while the concentration of the total phosphorus in the to-be-treated water was 10 mg/L, and 0.2 mg/L in the yielding water.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201910264781.8 | Apr 2019 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2020/082655 | 4/1/2020 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2020/200215 | 10/8/2020 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 20010030160 | Wechsler | Oct 2001 | A1 |
| 20150191374 | Schwarz et al. | Jul 2015 | A1 |
| 20160052808 | Huang | Feb 2016 | A1 |
| Number | Date | Country |
|---|---|---|
| 102884010 | Jan 2013 | CN |
| 103570114 | Feb 2014 | CN |
| 103626293 | Mar 2014 | CN |
| 104876306 | Sep 2015 | CN |
| 107697987 | Feb 2018 | CN |
| 109851144 | Jun 2019 | CN |
| Entry |
|---|
| Li et al., “Premagnetization for Enhancing the Reactivity of Multiple Zerovalent Iron Samples toward Various Contaminants”, Environmental Science & Technology, Nov. 17, 2015, pp. 14401-14408. |
| Number | Date | Country | |
|---|---|---|---|
| 20220194824 A1 | Jun 2022 | US |
