A water treatment method based on manganese-sulfur oxidation system

Abstract

The present invention discloses a water treatment method based on a manganese-sulfur oxidation system, and a heterogeneous manganese-sulfur oxidation system, wherein the oxidation system includes a liquid phase in which a water-soluble Mn(VII) source is dissolved; and also includes a gas phase containing S(IV) gas. The present invention constructs a heterogeneous Mn(VII) / S(IV) system so that the redox reaction between Mn(VII) and S(IV) is carried out at the heterogeneous interface of the gas / liquid interface. At the heterogeneous interface where the reaction occurs, S(IV) is locally excessive, which can promote the rapid progress of the redox reaction and generate highly active Mn(III) intermediates and sulfite radicals (SO3 ‑ •), and then react with the target pollutants to achieve effective oxidation and degradation of target pollutants, especially odorous organic pollutants and good water treatment effects.

Description

Technical Field

[0001] The invention belongs to the technical field of pollutant treatment, and in particular relates to a water treatment method based on a manganese-sulfur oxidation system. Background Art

[0002] The removal of odorous organic pollutants is an important issue in current water treatment technology. For example, the current water quality indicators include two extended indicators of sensory properties, namely the content of 2-methylisoborneol and geosmin, both of which have a limit of 10ng / L. Ensuring that 2-methylisoborneol and geosmin in water bodies are below the limit is crucial to ensuring the safety of drinking water. These two pollutants are mainly produced by the metabolism of algae, actinomycetes and other microorganisms in water. They have a certain volatility and can be detected by human sense of smell at low concentrations, causing the water body to produce an unpleasant earthy smell. It is a common source of odor in drinking water and has a serious negative impact on water quality and taste. At the same time, 2-methylisoborneol (2-MIB, C 11 H 20 Oh, ) and geosmin (GSM, C 12 H 22 Oh, ) are also extremely difficult to remove organic pollutants in natural water bodies. Both are saturated alicyclic tertiary alcohols. They are not easily oxidized under neutral and alkaline conditions. Under acidic conditions, they can be dehydrated to olefins, and then the carbon-carbon bonds are broken to form small molecular compounds. However, the content of both in natural water bodies is extremely low, and it is almost impossible to effectively remove them through ordinary chemical oxidation methods.

[0003] Advanced oxidation methods have shown good degradation effects in removing 2-methylisoborneol and geosmin, but there are still some problems, such as the high cost of ozone degradation of organic matter, low utilization rate and strong selectivity of ozone reaction with organic matter; the easy decomposition of hydrogen peroxide in the UV / hydrogen peroxide combination technology; the UV / chlorine combination pretreatment technology will increase disinfection by-products; the UV / persulfate reaction time is long and the cost is high.

[0004] The newly developed potassium permanganate / sodium bisulfite system in recent years has a high-intensity oxidation capacity. According to research, the system can degrade organic matter within milliseconds, and its oxidation capacity is much higher than that of potassium permanganate alone. The reaction intermediate Mn(Ⅲ) has extremely high oxidation activity and can degrade the target organic matter within milliseconds. In practical applications, it only requires simple addition of reagents, and the investment in fixed facilities and corresponding equipment is very small, which is very beneficial to the actual transformation of water plants. For example, a study disclosed that a certain amount of permanganate was added to the water to be treated for mixing, and solid sulfite was added and fully mixed after mixing, and the reaction lasted for 5 to 20 minutes. After the sulfite was dissolved and reacted, the water sample entered the subsequent precipitation and filtration equipment for solid-liquid separation; this method constructed a homogeneous Mn(VII) / S(Ⅳ) oxidation system with permanganate and solid sulfite, and controlled the reaction rate by controlling the solid dissolution rate. There are also studies that disclose adding a reducing agent, bisulfite, to the water to be treated, adjusting the pH to 3-7, and then adding an oxidizing agent, potassium permanganate; this method achieves ultra-fast removal of organic pollutants in water by rapidly producing a highly active oxidizing agent, Mn(III) (non-complexed state), and constructs a homogeneous Mn(VII) / S(IV) oxidation system with permanganate and bisulfite, requiring the addition of an excess of bisulfite and consuming a large amount of reagents to adjust the pH. A study disclosed a water treatment agent composed of potassium permanganate, a large amount of chelating agent and an inducer such as sulfite, wherein the chelating agent can form a coordination complex with the intermediate manganese produced by potassium permanganate oxidizing organic matter, thereby enhancing the ability of potassium permanganate to oxidize and degrade organic pollutants; the inducer can accelerate the production of highly active intermediate manganese, thereby increasing both the production rate of intermediate manganese and its utilization rate, thereby further enhancing the ability of potassium permanganate to oxidize and degrade organic pollutants; this method also constructs a homogeneous Mn(VII) / S(IV) oxidation system, which requires the addition of dozens of times more chelating agent.

[0005] In the above existing studies, homogeneous Mn(VII) / S(IV) oxidation systems were constructed by different methods. In these homogeneous systems, in order to generate Mn(III) intermediates and sulfite radicals (SO3 - •), excessive amounts of S(Ⅳ) agents, large amounts of Mn(Ⅲ) chelating agents and water pH adjusting agents are always added, which greatly increases the water production cost of the water plant, and the removal rate of the target organic pollutants is difficult to achieve the ideal effect. Summary of the invention

[0006] In order to overcome at least one of the problems existing in the above-mentioned prior art, one of the objects of the present invention is to provide a heterogeneous manganese-sulfur oxidation system. By utilizing this heterogeneous system, the removal rate of organic pollutants in water can be effectively improved and the water treatment cost can be greatly reduced.

[0007] A second object of the present invention is to provide an application of the above-mentioned heterogeneous manganese-sulfur oxidation system in water treatment.

[0008] A third object of the present invention is to provide a water treatment method based on a manganese-sulfur oxidation system.

[0009] In order to achieve the above object, the technical solution adopted by the present invention is:

[0010] The invention provides a heterogeneous manganese-sulfur oxidation system, which comprises a liquid phase in which a water-soluble Mn(VII) source is dissolved, and also comprises a gas phase containing S(IV) gas.

[0011] The present invention constructs a heterogeneous Mn(VII) / S(IV) system, in which the Mn(III) intermediates and sulfite radicals (SO3 - •) are intermediates that directly react with target pollutants, but both are extremely unstable and have a short lifespan in water. They need to be rapidly generated when S(Ⅳ) is in excess, and then rapidly react with target pollutants. In general homogeneous Mn(VII) / S(Ⅳ) systems, such as potassium permanganate-sodium bisulfite aqueous solution systems, excessive S(Ⅳ) will result in excessive sodium bisulfite remaining in the water, resulting in a waste of reagents and affecting the quality of drinking water.

[0012] The present invention can solve the problems in the prior art in a heterogeneous manner. Specifically, by introducing a gas phase containing S(IV) gas, a redox reaction occurs rapidly at the gas / liquid interface of the bubbles to generate Mn(III) intermediates and sulfite radicals (SO3 - •), and then react with the target pollutant. At this time, S(IV) is locally excessive at the gas / liquid interface where the reaction occurs. After completing the task of removing the target pollutant, basically no excess S(IV) remains in the water body.

[0013] In addition, water-soluble Mn(VII) sources have good oxidation ability and can effectively oxidize and degrade pollutants in water bodies. However, some pollutants in water bodies are not easily oxidized by Mn(VII) under neutral or alkaline conditions. Only under acidic conditions can carbon-carbon bonds break to form small molecular compounds. Some naturally polluted water bodies are usually weakly alkaline, with a pH value of about 7.5~9. In this environment, the oxidation ability of Mn(VII) is weak, and the reduction product is mainly manganese dioxide (MnO2). The standard electrode potential of Mn(VII) reduced to manganese dioxide under alkaline conditions is is 0.60V.

[0014] The present invention introduces a gas phase containing S(IV) gas, which can quickly dissolve in water and generate sulfurous acid (H2SO3), making the water acidic, thereby enhancing the oxidizing ability of the water-soluble Mn(VII) source. There is no need to add a large amount of acidic reagents for adjusting the pH value. The oxidizing ability of potassium permanganate is relatively strong in an acidic environment, and the reduction product is mainly divalent manganese ions (Mn 2+ ), the standard electrode potential of Mn(VII) reduction to manganese ion under acidic conditions It is 1.51V, which is significantly higher than the electrode potential under alkaline conditions, that is, the oxidation ability of Mn(VII) is significantly stronger under acidic conditions. In addition, since the oxidation reaction of Mn(VII) requires the consumption of acid, the water body can return to neutrality after the reaction is completed, and the water body will not become acidic due to the introduction of S(IV) gas, thus avoiding the addition of a large amount of acid and alkali to adjust the pH value during the treatment of drinking water, greatly saving the cost of reagents and water treatment. At the same time, since no or less reagents such as sulfite are used, irrelevant cations (such as sodium ions, calcium ions, etc.) will not be introduced, which meets the requirements of green conservation.

[0015] In the present invention, "water-soluble" means that the solubility of the substance in deionized water at 20°C is ≥ 500 mg / L; "water-insoluble" means that the solubility of the substance in deionized water at 20°C is < 500 mg / L.

[0016] Preferably, in the liquid phase, the concentration of the water-soluble Mn(VII) source is 2-10 mg / L; more preferably, 3-6 mg / L.

[0017] Preferably, in the liquid phase, the water-soluble Mn(VII) source is introduced in the form of water-soluble permanganate.

[0018] Preferably, the water-soluble permanganate includes at least one of potassium permanganate, sodium permanganate or ammonium permanganate; further preferably, the water-soluble permanganate is selected from potassium permanganate.

[0019] Preferably, a water-soluble S(IV) source is also dissolved in the liquid phase.

[0020] Preferably, the water-soluble S(IV) source comprises a water-soluble sulfite, a water-soluble bisulfite or a combination thereof.

[0021] Preferably, the water-soluble sulfite includes at least one of sodium sulfite, potassium sulfite or ammonium sulfite; further preferably, the water-soluble sulfite is selected from sodium sulfite (Na2SO3).

[0022] Preferably, the water-soluble bisulfite includes at least one of sodium bisulfite, potassium bisulfite or ammonium bisulfite; further preferably, the water-soluble bisulfite is selected from sodium bisulfite (NaHSO3).

[0023] Preferably, in the liquid phase, the concentration of the water-soluble S(IV) source is ≤10 mg / L; more preferably 1-10 mg / L; and even more preferably 4-8 mg / L.

[0024] Adding a water-soluble S(IV) source to the liquid phase can increase the source of S(IV) in the liquid phase. Adjusting its usage ratio can regulate the pH value in the liquid phase and improve the removal rate of target pollutants.

[0025] Preferably, the pH value of the liquid phase is 5 to 7; more preferably 5.5 to 6.5.

[0026] Preferably, the liquid phase further comprises a pH regulator; in some specific embodiments of the present invention, the pH regulator is selected from sodium dihydrogen phosphate (NaH2PO4).

[0027] Preferably, in the gas phase, the volume percentage of S(IV) gas is 5-100%; more preferably 5-50%; and even more preferably 5-30%.

[0028] The volume percentage of S(IV) gas can be adjusted according to different water treatment systems.

[0029] Preferably, in the gas phase, the S(IV) gas is introduced in the form of sulfur dioxide gas.

[0030] At normal temperature and pressure, 1 volume of water can absorb 40 volumes of sulfur dioxide gas. Therefore, it is only necessary to reasonably set the aeration volume of sulfur dioxide. The sulfur dioxide will all be dissolved in the water and react, and will not escape from the water, increasing safety risks.

[0031] Preferably, the gas phase further contains an oxygen-containing gas; in some specific embodiments of the present invention, the oxygen-containing gas includes oxygen or air; in some more specific embodiments of the present invention, the oxygen-containing gas is selected from air.

[0032] Since the gas / liquid interface of the bubbles is the reaction point for removing the target pollutants, increasing the gas / liquid interface can effectively improve the reaction efficiency. To this end, an optimal choice is to use sulfur dioxide-air mixed gas aeration, which can increase a large number of bubbles (increase the aeration volume) and extend the life of the bubbles (when pure sulfur dioxide is aerated, sulfur dioxide quickly dissolves in water and the bubbles disappear), greatly increasing the gas / liquid interface. In addition, oxygen in the air can also participate in the reaction at the gas / liquid interface and react with sulfite free radicals (SO3 - •) reacts to generate sulfate radicals (SO4 - •), enhance the ability to remove target pollutants and reduce the dosage of water-soluble Mn(VII) source.

[0033] Preferably, the mass ratio of the water-soluble Mn(VII) source to the S(IV) gas is 1:(1-5); more preferably 1:(1.5-4); and even more preferably 1:(2-3).

[0034] The second aspect of the present invention provides an application of the heterogeneous manganese-sulfur oxidation system described in the first aspect of the present invention in water treatment.

[0035] Preferably, the pollutants targeted by the water treatment include odorous organic pollutants; further preferably, the odorous organic pollutants include at least one of saturated alicyclic alcohols, sulfides, pyrazines, thiazoles or terpenes; further preferably, the odorous organic pollutants are selected from saturated alicyclic alcohols.

[0036] In some specific embodiments of the present invention, the pollutants targeted by the water treatment include 2-methylisoborneol and / or geosmin; in some more specific embodiments of the present invention, the pollutants targeted by the water treatment include 2-methylisoborneol and geosmin.

[0037] The heterogeneous manganese-sulfur oxidation system provided in the first aspect of the present invention can be particularly used to oxidatively degrade odorous organic pollutants such as 2-methylisoborneol and geosmin, thereby eliminating the unpleasant earthy smell in drinking water sources.

[0038] Preferably, the concentration of 2-methylisoborneol in the water to be treated is 5-100 ng / L; more preferably, it is 15-40 ng / L.

[0039] Preferably, the concentration of geosmin in the water treated is 5-100 ng / L; more preferably, it is 15-40 ng / L.

[0040] The third aspect of the present invention provides a water treatment method based on a manganese-sulfur oxidation system, comprising the following steps: mixing the water body to be treated with a water-soluble Mn(VII) source to form a liquid phase in which the water-soluble Mn(VII) source is dissolved; and then treating the liquid phase with a gas phase containing S(IV) gas to achieve oxidative degradation of target pollutants in the water body to be treated.

[0041] Preferably, the water treatment method described in the third aspect of the present invention adopts the heterogeneous manganese-sulfur oxidation system described in the first aspect of the present invention.

[0042] Preferably, the liquid phase is treated by a gas phase containing S(IV) gas by: 1) introducing a gas phase containing S(IV) gas into the liquid phase; or

[0043] 2) Dispersing and pouring the liquid phase into the gas phase containing the S(IV) gas.

[0044] The general drinking water pre-oxidation scheme is limited to drinking water raw water. When the water treatment method of the present invention treats the liquid through the gas phase, it can be used not only for raw water, but also for the process section before filtration. When the water treatment method of the present invention is applied to raw water, the dosage of water-soluble Mn (VII) source (such as potassium permanganate) is relatively large, which can kill most algae, and the oxidation products such as manganese dioxide and manganese sulfate can participate in flocculation; when applied to the front section of the filter tank, since the flocculation precipitation process removes most of the conventional pollutants in the water body and reduces the interference with the Mn (VII) / S (IV) system, the dosage of the agent can be reduced, and the product after oxidation is a small amount of manganese sulfate, potassium sulfate, etc., which can be removed when passing through the filter tank.

[0045] Preferably, the target pollutants in the water body to be treated include odorous organic pollutants; further preferably, the odorous organic pollutants include at least one of saturated alicyclic alcohols, sulfide substances, pyrazine substances, thiazole substances or terpene substances; further preferably, the odorous organic pollutants are selected from saturated alicyclic alcohols.

[0046] In some specific embodiments of the present invention, the target pollutants in the water body to be treated include 2-methylisoborneol and / or geosmin; in some more specific embodiments of the present invention, the target pollutants in the water body to be treated include 2-methylisoborneol and geosmin.

[0047] Preferably, the target pollutant content in the water to be treated is 5~200ng / L; more preferably, it is 30~100ng / L.

[0048] Preferably, the concentration of 2-methylisoborneol in the water to be treated is 5-100 ng / L; more preferably, it is 15-40 ng / L.

[0049] Preferably, the concentration of geosmin in the water to be treated is 5-100 ng / L; more preferably, it is 15-40 ng / L.

[0050] The beneficial effects of the present invention are as follows: the present invention constructs a heterogeneous Mn(VII) / S(IV) system, so that the redox reaction between Mn(VII) and S(IV) is carried out at the heterogeneous interface of the gas / liquid interface. At the heterogeneous interface where the reaction occurs, S(IV) is locally excessive, which can promote the rapid progress of the redox reaction and generate highly active Mn(III) intermediates and sulfite free radicals (SO3 - •), and then react with the target pollutants to achieve effective oxidation and degradation of the target pollutants, especially odorous organic pollutants and good water treatment effects. The heterogeneous manganese-sulfur oxidation system provided by the present invention has good application effects in water treatment. DETAILED DESCRIPTION

[0051] The content of the present invention is further described in detail below through specific examples. It should also be understood that the following examples are only used to further illustrate the present invention and cannot be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the principles set forth in the present invention all belong to the scope of protection of the present invention. The specific process parameters and the like in the following examples are also only examples within a suitable range, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific data exemplified below. The raw materials, reagents or devices used in the following examples and comparative examples, unless otherwise specified, can all be obtained from conventional commercial sources, or can be obtained by existing known methods.

[0052] In the embodiments of the present invention and the comparative examples, the actual raw water of a water plant in the south is used as the treatment object. The raw water is low-turbidity algae-containing reservoir water, with a turbidity of 3-4 NTU, a pH value of 7.0-7.5, an algae density of 40-50 million / L, a 2-methylisoborneol (2-MIB) content of 8-15 ng / L, and a geosmin (GSM) content of 5-10 ng / L.

[0053] In the examples and comparative examples of the present invention, the detection of 2-methylisoborneol (2-MIB) and geosmin (GSM) was carried out by headspace solid phase microextraction gas chromatography-mass spectrometry according to the "Standard Test Method for Drinking Water" (GB / T 5750.8-2023).

[0054] In the examples and comparative examples of the present invention, the content of sulfur dioxide in the mixed gas is measured by volume percentage.

[0055] Example 1

[0056] A water treatment method based on a manganese-sulfur oxidation system, the specific steps are as follows:

[0057] 1) Take the raw water to be treated, add standard odor substances 2-MIB and GSM to obtain spiked raw water. The content of 2-MIB in the spiked raw water is 40.3 ng / L, and the content of GSM is 20.8 ng / L.

[0058] 2) Add potassium permanganate (KMnO4) to the spiked raw water at a dosage of 4 mg / L. After mixing evenly, aerate the sulfur dioxide-air mixed gas, where the sulfur dioxide dosage is fixed at 12 mg / L. Adjust the air dosage so that the sulfur dioxide content in the mixed gas is 10% and 30% respectively.

[0059] 3) Then, the flocculant polyaluminium ferric chloride (PAFC) is added into the water body at a dosage of 20 mg / L, and the flotation effluent is obtained after being treated in the grid flocculation tank and the flotation tank.

[0060] The results showed that when the sulfur dioxide content in the mixed gas was 10%, the removal rates of 2-MIB and GSM were higher. The flotation effluent measured: 2-MIB content was 8.8 ng / L, the removal rate was 78.2%; GSM content was 6.5 ng / L, the removal rate was 68.8%. When the sulfur dioxide content in the mixed gas was 30%, the flotation effluent measured: 2-MIB content was 15.7 ng / L, the removal rate was 61.0%; GSM content was 9.8 ng / L, the removal rate was 52.9%.

[0061] Example 2

[0062] A water treatment method based on a manganese-sulfur oxidation system, the specific steps are as follows:

[0063] 1) Take the raw water to be treated, add standard odor substances 2-MIB and GSM to obtain spiked raw water. The content of 2-MIB in the spiked raw water is 45.1 ng / L, and the content of GSM is 23.9 ng / L.

[0064] 2) Add potassium permanganate (KMnO4) to the spiked raw water at a dosage of 4 mg / L, mix well and aerate with a sulfur dioxide-air mixed gas. The sulfur dioxide content in the mixed gas is 10%, and the sulfur dioxide dosage is 12 mg / L; and add sodium bisulfite (NaHSO3) at a dosage of 6 mg / L.

[0065] 3) Then, the flocculant polyaluminium ferric chloride (PAFC) is added into the water body at a dosage of 20 mg / L, and the flotation effluent is obtained after being treated in the grid flocculation tank and the flotation tank.

[0066] The flotation effluent was measured to have: 2-MIB content of 6.4 ng / L, with a removal rate of 85.8%; GSM content of 5.1 ng / L, with a removal rate of 78.7%.

[0067] Comparative Example 1

[0068] A conventional water treatment method, the specific steps are as follows:

[0069] 1) Take the raw water to be treated, add standard odor substances 2-MIB and GSM to obtain spiked raw water. The content of 2-MIB in the spiked raw water is 43.6 ng / L, and the content of GSM is 22.5 ng / L.

[0070] 2) Use a set of processing capacity of 10m 3 / h pilot plant, added flocculant polyaluminium ferric chloride (PAFC) into the spiked raw water, the dosage was 20mg / L, and the flotation effluent was obtained after treatment in the grid flocculation tank and flotation tank.

[0071] The flotation effluent was measured to have: 2-MIB content of 38.3 ng / L, with a removal rate of 12.2%; GSM content of 20.6 ng / L, with a removal rate of 8.4%.

[0072] Comparative Example 2

[0073] A water treatment method for a homogeneous oxidation system, the specific steps are as follows:

[0074] 1) Take the raw water to be treated, add standard odor substances 2-MIB and GSM to obtain spiked raw water. The content of 2-MIB in the spiked raw water is 43.6 ng / L, and the content of GSM is 22.5 ng / L.

[0075] 2) Potassium permanganate (KMnO4) was added to the spiked raw water in sequence at a dosage of 4 mg / L and sodium bisulfite (NaHSO3) at a dosage of 20 mg / L.

[0076] 3) Then, the flocculant polyaluminium ferric chloride (PAFC) is added into the water body at a dosage of 20 mg / L, and the flotation effluent is obtained after being treated in the grid flocculation tank and the flotation tank.

[0077] The flotation effluent measured: 2-MIB content was 20.9 ng / L, with a removal rate of 52.1%; GSM content was 12.6 ng / L, with a removal rate of 44.0%.

[0078] In summary, the present invention constructs a heterogeneous Mn(VII) / S(IV) system, so that the redox reaction between Mn(VII) and S(IV) is carried out at the heterogeneous interface of the gas / liquid interface. At the heterogeneous interface where the reaction occurs, S(IV) is locally excessive, which can promote the rapid redox reaction and generate highly active Mn(III) intermediates and sulfite radicals (SO3 - •), and then react with the target pollutants to achieve effective oxidation and degradation of the target pollutants, especially odorous organic pollutants and good water treatment effects. The heterogeneous manganese-sulfur oxidation system provided by the present invention has good application effects in water treatment.

Claims

1. A water treatment method based on a manganese-sulfur oxidation system, characterized in that: The following steps are involved: The water body to be treated is mixed with a water-soluble Mn(VII) source to form a liquid phase in which the water-soluble Mn(VII) source is dissolved; the liquid phase is then treated with a gas phase containing S(IV) gas to achieve oxidative degradation of target pollutants in the water body to be treated; the gas phase also contains oxygen-containing gas; the volume percentage of S(IV) gas in the gas phase is 5-50%; In the liquid phase, the concentration of the water-soluble Mn(VII) source is 2-10 mg / L; The mass ratio of the water-soluble Mn(VII) source to the S(IV) gas is 1:(1-5); In the liquid phase, a water-soluble Mn(VII) source is introduced in the form of a water-soluble permanganate; In the gas phase, S(IV) gas is introduced in the form of sulfur dioxide gas; The pH value of the liquid phase is 5-7.

2. The water treatment method according to claim 1, characterized in that: The water-soluble permanganate includes at least one of potassium permanganate, sodium permanganate or ammonium permanganate.

3. The water treatment method according to claim 1, characterized in that: A water-soluble S(IV) source is also dissolved in the liquid phase; the water-soluble S(IV) source includes water-soluble sulfite, water-soluble bisulfite or a combination thereof; in the liquid phase, the concentration of the water-soluble S(IV) source is ≤10 mg / L.

4. The water treatment method according to claim 1, characterized in that: The target pollutants include odorous organic pollutants; the odorous organic pollutants include at least one of saturated alicyclic alcohol substances, sulfide substances, pyrazine substances, thiazole substances or terpenoid substances.

5. The water treatment method according to claim 1, characterized in that: The specific method of treating the liquid phase with a gas phase containing S(IV) gas is: 1) introducing a gas phase containing S(IV) gas into the liquid phase; or, 2) Dispersing and pouring the liquid phase into the gas phase containing S(IV) gas.

6. The water treatment method according to claim 1, characterized in that: The target pollutant content in the water to be treated is 5~200ng / L.