KR100743116B1 - Manufacturing method and apparatus of chlorine dioxide using inorganic acid hydrocloric acid and sulfuric acid and sodium hypochloride at sea water for ship ballast water treatment - Google Patents

Abstract

A method and an apparatus for manufacturing chlorine dioxide by using inorganic acid hydrochloric acid, sulfuric acid and sodium hypochlorite at sea water for ship ballast water treatment are provided to improve the purity and the yield of chlorine dioxide by easily generating chlorine dioxide with fresh water or sea water, and controlling concentration of chlorine dioxide according to an amount of compounds. An inlet(10) is formed to introduce sea water. A first input device(20) is connected with the inlet for putting oxalic acid, boric acid, phosphoric acid, silica sodium fluoride, sulphuric acid, sodium oxalate, sodium metaborate, potassium borate, sodium meta silicate, disodium phosphate, and sodium sulphate. A first line mixer(30) is connected with the first input device and mixes the sea water with the oxalic acid, boric acid, phosphoric acid, silica sodium fluoride, sulphuric acid, sodium oxalate, sodium metaborate, potassium borate, sodium meta silicate, disodium phosphate, and sodium sulphate. A second input device(40) is connected with the first line mixer and puts chlorite, phosphoric acid, hydrochloric acid, and sodium hypochlorite. A second line mixer(50) is connected with the second input device for mixing the chlorite, phosphoric acid, hydrochloric acid, and sodium hypochlorite. A suction pump(60) is connected with the second line mixer for sucking a chlorine dioxide sea water solution. A discharge port(70) discharges the sucked chlorine dioxide sea water solution. The second input device selectively includes a chlorite input device(41), an inorganic acid input device(42), and a sodium hypochlorite input device.

Description

(Manufacturing Method and Apparatus of Chlorine Dioxide using inorganic acid hydrocloric acid and sulfuric acid and Sodium Hypochloride at Sea Water for Ship Ballast Water Treatment}

1 is a schematic view showing a device for producing a conventional chlorine dioxide,

Figure 2 is a schematic diagram showing a chlorine dioxide production apparatus using chlorite and inorganic acid hydrochloric acid or sulfuric acid according to the present invention,

3 is a schematic diagram showing an apparatus for producing chlorine dioxide using chlorite and hypochlorite and inorganic acid hydrochloric acid or sulfuric acid according to the present invention,

 4 is a flowchart illustrating a chlorine dioxide production method according to FIGS. 2 and 3.

<Description of the symbols for the main parts of the drawings>

10: inlet 20: primary injection device

30, 50: 1st, 2nd line mixer 40: 2nd input device

41: chlorite input device 42: inorganic acid input device

43: hypochlorite input device 60: suction pump

70 outlet

The present invention relates to a method and apparatus for producing chlorine dioxide using seawater useful for ballast water treatment of ships.

Chlorine dioxide has strong oxidizing, bactericidal and deodorizing properties. Unlike other chlorine disinfectants, chlorine dioxide does not produce carcinogenic substances such as trihalomethanes (THMs), haloacetic acid (HAAs), haloacetonitrile (HANs), and other organic compounds. Since it does not react with the compound, it does not make an organic chlorine compound, so it is used in tap water purification plants and has the characteristics of an eco-friendly disinfectant that is quickly decomposed by sunlight or temperature and has no residual.

As a conventional apparatus for producing chlorine dioxide, as shown in FIG. 1, when the pressure of the dilution water is increased in the booster pump 210, the dilution water (about 3 to 6 atmospheres) of high pressure passes through the narrow nozzle of the ejector 220. When the injection is carried out (more than 20m / s) the decompression phenomenon occurs inside the ejector, it is prepared by injecting chlorite solution and chlorine at the same time through the tubes 230, 240 installed on the side of the ejector using the decompression.

Conventional methods for preparing chlorine dioxide using fresh water as reaction and dilution water are well known in many literatures and patents, but the method of using sea water as reaction water is not known.

So far known chlorine dioxide production method is to produce chlorine dioxide by producing a large capacity (tens of hundreds to hundreds of tons) of salts by high temperature electrolysis to synthesize chlorate and reacting the salts with reducing agent sulfurous acid gas or hydrochloric acid solution.

Reducing chlorate (NaClO ₃ ) to sulfur dioxide (SO ₂ ) under sulfuric acid

Chlorochloric acid (HClO ₂ ) is produced.

In addition, when chlorate is reduced to hydrochloric acid under hydrochloric acid, chlorite and hypochlorous acid (HClO) are produced. Their chemical reactions are as follows.

2NaClO ₃ + H ₂ SO ₄ → 2HClO ₃ + Na ₂ SO ₄

HClO ₃ + H ₂ SO ₃ → HClO ₂ + H ₂ SO ₄

HClO ₃ + HClO ₂ → 2ClO ₂ + H ₂ O

2NaClO ₃ + 2HCl → 2HClO ₃ + 2NaCl

HClO ₃ + HCl → HClO ₂ + HClO

HClO ₃ + HClO ₂ → 2ClO ₂ + H ₂ O

HClO + HCl → Cl ₂ + H ₂ O

(This process must be separated because chlorine dioxide and chlorine gas are produced simultaneously.)

As shown in Schemes 1 and 2 above, chlorate is newly produced by acidic reducing agent SO ₂ or HCl under acidic acid, and chloric acid (HClO ₃ ) and newly generated chlorite (HClO ₂ ) are condensation reaction at constant acidity. Chlorine (ClO ₂ ) and water are produced.

Where chlorine dioxide requires tens to hundreds of kilograms per day, unlike chlorine dioxide, the chlorite is oxidized with oxidant to produce chloric acid, which is condensed with chlorine acid, producing chlorine dioxide and water.

As described above, three methods are known for preparing chlorine dioxide using chlorite as a starting material.

<Method 1>

Inorganic acid (HCl or H ₂ SO ₄ ) and chlorite react to form chlorite.

NaClO ₂ + HCl → HClO ₂ + NaCl

2NaClO ₂ + H ₂ SO ₄ → 2HClO ₂ + Na ₂ SO ₄

Heterogeneous decomposition reactions occur depending on the concentration of chlorite and the amount and concentration of inorganic acid.

2HClO ₂ → HClO ₃ + HClO

The hypochlorous acid produced at this time reacts with chlorous acid to form chloric acid.

HClO + HClO ₂ → HClO ₃ + HCl

The newly produced two molecules of chloric acid condensate with two molecules of chlorine acid to produce four molecules of chlorine dioxide.

2HClO ₃ + 2HClO ₂ → 4ClO ₂ + 2H ₂ O

If we sum up the above reaction

5NaClO ₂ + 4HCl → 4ClO ₂ + 5NaCl + 2H ₂ O

5NaClO ₂ + 2H ₂ SO ₄ → 4ClO ₂ + 2Na ₂ SO ₄ + NaCl + 2H ₂ O

<Method 2>

How hypochlorite and inorganic acids (HCl or H2SO4) oxidize chlorite to chloric acid to synthesize chlorine dioxide

2NaClO ₂ + NaClO + 2HCl → 2ClO ₂ + 3NaCl + H ₂ O

2NaClO ₂ + NaClO + H ₂ SO ₄ → 2ClO ₂ + Na ₂ SO ₄ + NaCl + H ₂ O

In these two formulas, hypochlorite and chlorite are produced by hypochlorite and chlorite by acid, which hypochlorite oxidizes chlorite. At this time, the newly produced chloric acid condensates with chlorine acid to produce chlorine dioxide and water.

<Method 3>

How to oxidize chlorite to chlorine.

In the chlorine oxidation method, chlorine is hydrolyzed by fresh water to produce hypochlorous acid and hydrochloric acid, hydrochloric acid turns chlorite into chlorite, and the resulting chlorite reacts with hypochlorous acid to produce chloric acid.

The produced chloric acid condenses with chlorous acid to produce chlorine dioxide and water.

Their chemical reactions are as follows.

Cl ₂ + H ₂ O → HClO + HCl

NaClO ₂ + HCl → HClO ₂ + NaCl

HClO + HClO ₂ → HClO ₃ + HCl

NaClO ₂ + HCl → HClO ₂ + NaCl

HClO ₃ + HClO ₂ → 2ClO ₂ + H ₂ O

In summary,

2NaClO ₂ + Cl ₂ → 2ClO ₂ + 2NaCl

As shown in Synthesis Methods 1, 2, and 3 above, hypochlorite, chlorite, and chloric acid are inevitably required when chlorine is synthesized from chlorite as a starting compound. At this time, the amount and concentration of chlorite and acid are uniform, and ClO ₂ as well as ClO ₂ ￣, ClO ₃ ￣, Cl ₂ , and Cl 함께 are produced together with rapid mixing and reaction temperature. It is very important to establish

In other words, these reactions can minimize the above side reactions by controlling the ratio and concentration of the reactants, the method of rapid and uniform mixing of the reactants, and the proper acidity and concentration, so that a high purity and high yield chlorine dioxide solution can be obtained. . In addition, these inorganic compounds are completely dissolved in fresh water, and the reaction proceeds very rapidly because the redox potential between the compounds is very different.

In addition, the fresh water contained very few alkaline earth metals in the tens of mg units, so it was possible to produce high purity and high yield chlorine dioxide solution because it did not produce poorly soluble hypochlorite or chlorite. In contrast, ships sailing through the sea use ballast water as seawater, and strong oxidizing and disinfecting agents are needed to remove the species of living species. It is ideal to prepare the required compounds directly from the sea using seawater as the dilution water for the reaction and to treat the ballast water. However, many kinds of inorganic salts are dissolved in seawater. Especially, alkaline earth metal salts such as magnesium (Mg ⁺⁺ ) and calcium (Ca ⁺⁺ ) react with poorly soluble hypochlorite to react with MgCl (ClO), Mg (ClO) ₂ , Reacts with CaCl (ClO), Ca (ClO) ₂ or chlorite to produce Mg (ClO ₂ ) ₂ , Ca (ClO ₂ ) _2, etc., and slows down the rate of chlorine dioxide formation reaction that should proceed very quickly As a result, the quantitative ratios and concentrations of the reaction compounds are different, so that a secondary reactant is generated, which significantly lowers the yield of chlorine dioxide.

As described above, in the manufacture of chlorine dioxide for ballast water treatment of ships, alkaline earth metals are very small (mg units) when freshwater is used as a reaction and dilution water by oxidizing chlorite to synthesize chloric acid. Due to its dissolution, the reaction proceeds well to produce chlorine dioxide with high purity and high yield.However, when dilution and reaction water are used, alkali earth metals dissolved in seawater, hypochlorous acid and chloric acid react to form poorly soluble earth metal salts. As a result, the reaction rate is remarkably suppressed to produce low yield and low purity chlorine dioxide, and many byproducts are generated.

In other words, many inorganic salts are dissolved in seawater. Among them, alkaline earth metal salts such as magnesium and calcium participate in the production and production of chlorine dioxide to suppress the reaction rate, and side reactions occur, which significantly reduces the yield and purity of chlorine dioxide. Since problems arise, specific acids or salts thereof are added to seawater in advance to make insoluble to insoluble earth metal salts so that they cannot participate in the chlorine dioxide generation reaction, thereby significantly improving the yield and purity of chlorine dioxide.

Therefore, in the present invention, in order to overcome this, specific acids or salts of these acids are pre-added to the seawater used as the reaction and dilution water, so that poorly soluble to insoluble earth metal salts are produced, and chlorite is instantaneously oxidized by hypochlorous acid. It is an object of the present invention to provide a manufacturing method and apparatus which can produce chlorine dioxide and water by causing condensation reaction with chlorine acid under acidic conditions, thereby producing chlorine dioxide and water.

The configuration of the present invention for achieving the above object is, in the chlorine dioxide production apparatus 100 for treating aquatic organisms, toxic vibrio cholera, E. coli and common microorganisms remaining in the ballast water of the vessel, for introducing the seawater Inlet 10 and connected to the inlet 10, oxalic acid, boric acid, phosphoric acid, fluorinated silicic acid, sulfuric acid or sodium oxalate, sodium metaborate, potassium borate, sodium metasilicate, disodium phosphate, sodium sulfate Oxalic acid, boric acid, phosphoric acid, fluorinated silicic acid, sulfuric acid, sodium oxalate, sodium metaborate, potassium borate, sodium metathesis connected to the primary input device 20 and the primary input device 20 It is connected to the primary line mixer 30 in which the silicate, disodium phosphate, and sodium sulfate are mixed, and the primary line mixer 30, and the chlorite, sulfur , A secondary line mixer 50 for mixing chlorite, sulfuric acid, hydrochloric acid, hypochlorite connected to the secondary dosing device 40, and a second input device 40 for inputting hydrochloric acid and hypochlorite. And a suction pump 60 connected to the secondary line mixer 50 to suck the chlorine dioxide seawater solution, and an outlet 70 for discharging the chlorine dioxide seawater solution sucked from the suction pump 60. The secondary input device 40 is characterized in that the chlorine acid input device 41 and the inorganic acid input device 42 and the hypochlorite input device 43 to which hydrochloric acid and sulfuric acid are added selectively comprises do.

In addition, the manufacturing method of the present invention for achieving the above object is the step of introducing the sea water (S10); Oxalic acid, boric acid, phosphoric acid, fluorinated silicic acid, sulfuric acid or sodium oxalate, sodium metaborate, potassium borate, sodium metasilicate, disodium phosphate, sodium sulfate were first introduced into the introduced seawater (S20) and ; (S30) first mixing the oxalic acid, boric acid, phosphoric acid, fluorinated silicic acid, sulfuric acid, sodium oxalate, sodium metaborate, potassium borate, sodium metasilicate, disodium phosphate, and sodium sulfate; A second step of adding chlorite, sulfuric acid, hydrochloric acid, hypochlorite, which is another compound, to the seawater and the earth metal salt produced by the first mixing step (S30); Secondly mixing chlorite, sulfuric acid, hydrochloric acid, hypochlorite, which is a second compound into seawater and earth metal salt, which are the primary mixtures (S50); Discharging the chlorine dioxide seawater solution produced by the second mixture through an intake pump (S60); oxalic acid, boric acid, phosphoric acid, fluorosilicate, sulfuric acid or sodium oxalate, sodium metaborate, Potassium borate, sodium metasilicate, disodium phosphate and sodium sulfate in the first step (S20) is used to remove alkali earth metals dissolved in seawater, oxalic acid, sodium metasilicate, phosphoric acid, sulfuric acid, fluorinated silicic acid and oxalic acid. It is characterized by adding sodium salt, disodium phosphate, sodium sulfate, and sodium metaborate.

In addition, the primary oxalic acid, boric acid, phosphoric acid, fluorinated silicic acid, sulfuric acid, sodium oxalate, sodium metaborate, potassium borate, sodium metasilicate, disodium phosphate, sodium sulfate in the primary mixing step (S30) Oxalic acid, boric acid, phosphoric acid, fluorinated silicic acid, sulfuric acid or sodium oxalate, sodium metaborate, potassium borate, sodium metasilicate, disodium phosphate, sodium sulfate and seawater added in the input step (S20) (30) It is characterized in that it is mixed in) to produce a poorly soluble to insoluble earth metal salt, chlorite, sulfuric acid, hydrochloric acid, hypochlorite which is another compound in the seawater and earth metal salt produced by the first mixing step (S30) In the second step (S40) of the chlorite disproportionately proceeds with the disproportionation reaction by acid of a certain concentration smoothly Chloric acid and hypochlorous acid are produced.

In addition, the introduced seawater is characterized in that used as dilution and reaction water.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Figure 2 is a schematic diagram showing an apparatus for producing chlorine dioxide using chlorite and inorganic acid hydrochloric acid or sulfuric acid according to the present invention. Figure 3 is an apparatus for producing chlorine dioxide using chlorite and hypochlorite and inorganic acid hydrochloric acid or sulfuric acid according to the present invention 4 is a flowchart illustrating a chlorine dioxide production process according to FIGS. 2 and 3.

When chlorine, hypochlorite or ozone is used as a disinfectant disinfectant for ballast water in ships, trihalomethanes (THMs), haloacetamides (HAAs), haloacetnitrils (HANs) and bromates (BrO) are carcinogens. _{3 iii} ) is produced and various chlorine compounds are produced. These disinfectants have good killing effect under neutrality, but the residual of disinfectants is low, but seawater has low alkalinity with low acidity of 8.5 with low acidity. do.

The present invention is to prepare a chlorine dioxide seawater solution by diluting the seawater in the hull as a reaction water with chlorine dioxide having strong oxidation, sterilization and disinfection deodorizing power that can kill various species living in the ballast water of the ship 2, 3, oxalic acid, boric acid, phosphoric acid, which may generate insoluble or insoluble salts by reacting with alkaline earth metals in seawater sucked before the first line mixer 30 as shown in the chlorine dioxide production apparatus. Sulfuric acid, fluorinated silicic acid, silicate and salts of these acids, which are well dissolved in seawater, are added to mix well with seawater in a line mixer to form poorly soluble to insoluble earth metal salts. When described with reference to:

2 is composed of a chlorine dioxide production apparatus using chlorite and inorganic acid hydrochloric acid or sulfuric acid is the inlet 10 for introducing seawater, and the primary input device connected to the inlet 10 to inject a specific acid or salt 20, a primary line mixer 30 connected to the primary input device 20 and mixed with seawater and the added compound, and two chloric acid inputs connected to the primary line mixer 30, respectively. The second dosing device 40 comprising the device 41 and the inorganic acid dosing device 42 and the second dosing device 40 connected to the second dosing device 40 and mixed with the compound It consists of a secondary line mixer 50, a suction pump 60 for sucking the mixture mixed in the secondary line mixer 50, and an outlet 70 for discharging chlorine dioxide.

In addition, Figure 3 is composed of a chlorine dioxide using a chlorite and hypochlorite and inorganic acid hydrochloric acid or sulfuric acid is composed of an inlet 10 for introducing the seawater for introducing the seawater, and is connected to the inlet 10 A primary line mixer 30 for introducing an acid or a salt, a primary line mixer 30 connected to the primary input device 20 and mixing seawater and an added compound, and the primary line mixer 30 And connected to the secondary input device 40, consisting of chlorine acid input device 41, inorganic acid input device 42 and hypochlorite input device 43, and the secondary input device 40 A secondary line mixer 50 connected to the secondary dosing device 40 for mixing the injected compound, a suction pump 60 connected to the secondary line mixer 50 for suctioning the mixture, and a dioxide It consists of an outlet 70 for discharging chlorine.

FIG. 4 is a flowchart showing a chlorine dioxide production method according to FIGS. 2 and 3.

First, the steps for preparing chlorine dioxide by the apparatus of Figure 2 and Figure 3 includes the step of introducing the seawater (S10), the first step of introducing a compound such as a specific acid or salt into the introduced seawater (S20) and First, the step of mixing the added compound (S30), the second step of adding another compound to the primary mixture (S40), and the second step of mixing the primary mixture and the second injected compound ( S50) and the produced chlorine dioxide is discharged through the suction pump (S60).

Here, in the manufacturing method of the production method of chlorine dioxide using chlorite and inorganic acid hydrochloric acid or sulfuric acid in the manufacturing method of the apparatus of FIG. 2, the disproportionation reaction of chlorite is proceeded smoothly by a specific concentration and the amount of acid and chloric acid. And hypochlorous acid are produced in a good yield.

Salts of these acids, which are well dissolved in acid or sea water, are added to the seawater sucked through the inlet port 10 in the primary input device 20 so that the seawater and the compound added in the primary line mixer 30 are mixed and simultaneously Soluble to insoluble earth metal salts are produced. The pre-treated reaction and dilution water are separated into two parts of 30 to 70 and the next reaction proceeds.

In this 30% by volume treated seawater, 60 wt% of the total required chlorite weight through the chlorite input device (41) and 66.6 Mol (Mol / L)% of the total required inorganic acid through the inorganic acid input device (42) were quantified. Into the pump (not shown) and the remaining 70% by volume of the treated seawater through another chlorine input device (41) the total required chlorite weight 40% by weight and the inorganic acid input device (42) the remaining required inorganic acid 33.4 Mol (Mol / L)% to the metering pump.

At high concentrations of chlorite and acid, chlorite and hypochlorous acid are rapidly generated due to disproportionate decomposition of chlorine acid, and chlorite and hypochlorous acid are produced without change in the portion of low concentration of chlorite and acid. As the two reactants are mixed in the second line mixer 50, chlorine dioxide is produced in high yield.

In addition, in the manufacturing method of the manufacturing apparatus of FIG. 3, the manufacturing method of the manufacturing apparatus of chlorine dioxide using chlorite and hypochlorite and inorganic acid hydrochloric acid or sulfuric acid is a primary line mixer in the seawater sucked through the inlet 10. (30) The salts of these acids, which are well dissolved in the acid or seawater, are added in the primary input device 20, and the insoluble earth metal salts are formed simultaneously with mixing of the seawater and the added compound in the primary line mixer 30. do. In the chlorite injector 41 and the hypochlorite injector 43, the chlorine and hypochlorite are mixed in the treated seawater with a mol ratio of 2: 1, and the inorganic acid injector 42 Equivalent acid is added to the treated seawater. In the second line mixer 50, the reaction proceeds simultaneously with mixing to generate chlorine dioxide. The generated chlorine dioxide seawater solution is discharged to the outside through the discharge port 70 by the suction pump (60).

Here, in the preparation of chlorine dioxide using seawater as a reaction and dilution water in the apparatus of FIGS. 2 and 3, alkaline earth metals dissolved in seawater are poorly soluble to insoluble to inhibit the reaction with hypochlorous acid or chlorite. In order to prepare the earth metal salt in advance, the acid or their salts raised above may be added to the primary input device 20 before the first line mixer 30 to smoothly generate the chlorine dioxide generation reaction as shown in FIGS. 2 and 3. In addition, the ratio and concentration of the reactants (acid, chlorine, chlorite, hypochlorite) and the method of rapid and uniform mixing of the reactants, the concentration and amount of the acid in order to produce less side reactions in the generation of chlorine dioxide It should be controlled to obtain high purity and high yield of chlorine dioxide.

The main points of the above-described manufacturing methods and apparatuses are that hypochlorous acid and chlorochloric acid cannot be reacted with alkali earth metals contained in seawater, so that specific or pre-added acids or salts of these acids are added to prevent the insoluble or insoluble earth metal salt. To generate.

Oxalic acid, boric acid, phosphoric acid, sulfuric acid, fluorinated silicic acid, silicate or salts of these acids which are well soluble in seawater are added to the seawater to be used in the present invention, and react with alkali earth metals dissolved in seawater to form poorly soluble to insoluble earth. Metal salts are produced, and these acids and salts are listed in more detail by oxalic acid, boric acid, phosphoric acid, fluorosilicates and sulfuric acid or salts of these acids such as sodium oxalate, sodium metaborate, potassium borate, sodium metasilicate, disodium phosphate , Sodium sulphate, etc., in the form of powder or solution, and automatically inject these acids or salts according to the amount of seawater prior to the first line mixer 30 to react with alkaline earth metals dissolved in the seawater. The formation of poorly soluble earth metals with hypochlorous acid or chlorous acid results in the yield of combustion Purity is dramatically improved.

In other words, in the preparation of chlorine dioxide seawater solutions for the ballast water treatment of ships, the use of seawater as a solvent and dilution water can suppress the reaction of alkaline earth metals dissolved in seawater with hypochlorous acid or chlorite. As shown in 2 and 3, various acids or salts of those acids are reacted with alkali earth metals dissolved in seawater prior to the first line mixer 30 to form insoluble or insoluble alkaline earth metal salts in advance. .

The invention is explained in more detail by way of examples. However, these examples are described to aid the understanding of the present invention and do not limit the content and scope of the invention.

<Example 1>

To the filtered seawater (1 L / min) 20 g / min of 40% by weight sodium metasilicate solution is introduced into the metering pump prior to the line mixer. This silicate compound is mixed with seawater uniformly in a mixer and at the same time insoluble earth metal salts are formed.

20.1 g / min of chlorite (25% by weight) and 7.72 g / min of hydrochloric acid (35% by weight) are respectively added to 300 ml / min of the treated seawater by a pump (not shown).

In addition, 13.4 g / min of chlorite (25% by weight) and 3.9 g / min of hydrochloric acid (35% by weight) are respectively injected into the treated seawater 700 ml / min by a pump (not shown).

A reaction solution and B reaction solution are uniformly mixed in the second line mixer 50 of FIG. 1 and chlorine dioxide is generated, and the chlorine dioxide seawater solution is discharged to the outside by the suction pump 60, and the yield is 92%. .

This example also covers all acid and salt examples listed above.

<Example 2>

To 1 l / min of filtered seawater is added by pump with 21.3 g / min of 40% by weight disodiumhydrogenphosphate. The compound added in the primary input device 20 is uniformly mixed in sea water and the primary line mixer 30, and insoluble earth metal salts are produced. A solution of 26.8 g / min chlorite (25% by weight) and 21.9 g / min hypochlorite (12% by weight) in 1 liter / min of treated seawater was injected into the primary treated seawater with a pump (not shown). 7.7 g / min hydrochloric acid (35% by weight) is injected into the same seawater. These three reactants are uniformly mixed in the secondary line mixer 50 and chlorine dioxide is generated at the same time. At this time, the generated chlorine dioxide seawater solution is discharged to the outside by the suction pump 60, the yield is 93%.

This example also applies to all of the acids and salts listed above.

Although the preferred embodiment according to the present invention has been described above, it will be understood by those skilled in the art that various changes and modifications are possible, but all belong to the scope of the present invention can be seen through the appended claims. will be.

As described in detail above, the present invention has a stronger killing effect than these chlorine compounds regardless of acidity, is unstable to light or temperature, has no residue and does not make by-products, so it is easy to use fresh water as well as fresh water as well as seawater. It can be generated by a simple device, and it is economical and can adjust the concentration of chlorine dioxide according to the amount of compound injected into the same generator as needed.Alkaline earth metal dissolved in seawater is made into insoluble earth metal salt to make chlorine or hypochlorous acid. It does not react with chloric acid, thereby increasing the yield and purity of chlorine dioxide.

Claims (7)

In the chlorine dioxide production apparatus 100 for treating aquatic organisms, toxic vibrio cholera, E. coli and general microorganisms remaining in the ballast water of the vessel, Inlet 10 for introducing seawater, and connected to the inlet 10, oxalic acid, boric acid, phosphoric acid, fluorinated silicic acid, sulfuric acid or sodium oxalate, sodium metaborate, potassium borate, sodium metasilicate, disodium phosphate , A primary injector 20 for injecting sodium sulfate and oxalic acid, boric acid, phosphoric acid, fluorinated silicic acid, sulfuric acid, sodium oxalate, sodium metaborate, Potassium borate, sodium metasilicate, disodium phosphate, sodium sulfate is mixed with the primary line mixer 30, the primary line mixer 30 is connected to the two chlorite, sulfuric acid, hydrochloric acid, hypochlorite A secondary line mixer 50 for mixing chlorite, sulfuric acid, hydrochloric acid, hypochlorite connected to the secondary input device 40, the secondary input device 40, and the secondary line; It is connected to the stand 50 is configured to include a suction pump 60 for sucking the chlorine dioxide seawater solution, and a discharge port 70 for discharging the chlorine dioxide seawater solution sucked from the suction pump 60 Chlorine dioxide production apparatus using inorganic acid hydrochloric acid, sulfuric acid and hypochlorite in seawater for treatment of ship ballast water. The method of claim 1, The secondary dosing device 40 is a vessel ballast water treatment, characterized in that the chlorine acid input device 41 and the inorganic acid input device 42 and the hypochlorite input device 43 into which hydrochloric acid and sulfuric acid are introduced. Chlorine dioxide production apparatus using inorganic acid hydrochloric acid and sulfuric acid and hypochlorite in seawater for. In the method for producing chlorine dioxide for treating aquatic organisms, toxic vibrio cholera, Escherichia coli and common microorganisms remaining in the ballast water of the vessel, Sea water flows in (S10); Oxalic acid, boric acid, phosphoric acid, fluorinated silicic acid, sulfuric acid or sodium oxalate, sodium metaborate, potassium borate, sodium metasilicate, disodium phosphate, sodium sulfate were first introduced into the introduced seawater (S20) and ; (S30) first mixing the oxalic acid, boric acid, phosphoric acid, fluorinated silicic acid, sulfuric acid, sodium oxalate, sodium metaborate, potassium borate, sodium metasilicate, disodium phosphate, and sodium sulfate; A second step of adding chlorite, sulfuric acid, hydrochloric acid, hypochlorite, which is another compound, to the seawater and the earth metal salt produced by the first mixing step (S30); Secondly mixing chlorite, sulfuric acid, hydrochloric acid, hypochlorite, which is a second compound into seawater and earth metal salt, which are the primary mixtures (S50); Discharging the chlorine dioxide seawater solution produced by the second mixture through a suction pump (S60); chlorine dioxide production using inorganic acid hydrochloric acid and sulfuric acid and hypochlorite in seawater for ship ballast water treatment, characterized in that the production Way . The method of claim 3, wherein Oxalic acid, boric acid, phosphoric acid, fluorinated silicic acid, sulfuric acid or sodium oxalate, sodium metaborate, potassium borate, sodium metasilicate, disodium phosphate, sodium sulfate are introduced into the seawater (S20). In order to remove dissolved alkaline earth metals, ship ballast water treatment is characterized by adding oxalic acid, sodium metasilicate, phosphoric acid, sulfuric acid, fluorinated silicic acid and sodium oxalate, disodium phosphate, sodium sulfate, and sodium methaborate. Method for preparing chlorine dioxide using inorganic acid hydrochloric acid, sulfuric acid and hypochlorite in seawater. The method of claim 3, wherein The first mixing step (S30) of the oxalic acid, boric acid, phosphoric acid, fluorinated silicic acid, sulfuric acid, sodium oxalate, sodium metaborate, potassium borate, sodium metasilicate, disodium phosphate, sodium sulfate (S30) Oxalic acid, boric acid, phosphoric acid, fluorinated silicic acid, sulfuric acid or sodium oxalate, sodium metaborate, potassium comrate, sodium metasilicate, disodium phosphate, sodium sulfate and seawater added in (S20) in the first line mixer (30) A process for producing chlorine dioxide using inorganic acid hydrochloric acid, sulfuric acid and hypochlorite in seawater for treatment of ship ballast water, characterized in that it is mixed with to form insoluble to insoluble earth metal salts. The method of claim 3, wherein The second step of adding another compound chlorite, sulfuric acid, hydrochloric acid, hypochlorite to the seawater and the earth metal salt produced by the first mixing step (S30) (S40) is uneven by the acid of a certain concentration A process for producing chlorine dioxide using inorganic acid hydrochloric acid, sulfuric acid and hypochlorite in seawater for treatment of ballast water, characterized in that the decomposition reaction proceeds smoothly to produce chloric acid and hypochlorous acid. The method of claim 3, wherein The introduced seawater is a method for producing chlorine dioxide using inorganic acid hydrochloric acid and sulfuric acid and hypochlorite in seawater for treatment of ship ballast water, characterized in that used as dilution and reaction water.

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