KR101285451B1 - Measuring device, monitoring method and monitoring system of total residual oxidants(tro) concentration within ballast water - Google Patents

Abstract

Provided is a measuring device for the concentration of TRO that can monitor the residual oxidant (TRO) concentration in the ballast water. In addition, the TRO measuring device monitors the TRO concentration in the ballast water treatment system.
It is a TRO monitor (1) which measures TRO density | concentration in ballast water by DPD absorption photometry. This TRO monitor 1 monitors the TRO concentration at the time of discharge of ballast water in the ballast water treatment system which processes the ballast water taken into a ship. In a system for treating ballast water using sodium hypochlorite, the TRO concentration is monitored, and the amount of sodium hypochlorite and the amount of neutralizer that neutralizes the TRO is controlled based on the measured value of the TRO concentration of the TRO monitor (1). . Moreover, in the system which treats ballast water using ozone, the procedure of the drainage process of ballast water is controlled based on the measured value of TRO density | concentration of the TRO monitor 1.

Description

MEASURING DEVICE, MONITORING METHOD AND MONITORING SYSTEM OF TOTAL RESIDUAL OXIDANTS (TRO) CONCENTRATION WITHIN BALLAST WATER}

The present invention relates to a technique for monitoring the concentration of TRO in ballast water using a measuring device for measuring the concentration of TRO in ballast water.

Large cargo ships, such as container ships and tankers, pump up the ballast water at the starting port and store it in tanks in the ship at the departure port, and prevent the hull from rising during the flight, and discharge the ballast water at the arrival port. have. At that time, fauna and flora contained in ballast water, fragments of seaweed, larvae and eggs such as endogenous organisms and fish are moved and spread with the ballast water into a new environment, and are not originally reproduced in the area. This may adversely affect the ecosystem and cause problems around the world.

The ballast water problem is centered on the International Maritime Organization (IMO), and international discussions have been under way since the 1980s, and in a meeting held in London in February 2004, the ballast water and sediment International Convention for Regulation and Management ”(the Ballast Water Management Convention) has been adopted. The treaty indicates the ballast water discharge standard in ships and sets the obligation to mount the ballast water treatment system. The ballast water treatment system generally includes (1) seawater collection to kill the aquatic organisms in the seawater, (2) to store the treated seawater in the ballast tank, and (3) After monitoring, take steps such as discharge to the sea.

As a method of removing aquatic organisms in this ballast water, for example, a method of injecting sodium hypochlorite (for example, Non Patent Literature 1), a method consisting of a coagulation separation process and a magnetic separation process (for example, a patent) Document 1) and the method which combined the physical crushing mechanism and sterilization by ozone (for example, patent document 2, 3, nonpatent literature 2), etc. are mentioned.

In IM0, the use of active substances in treatment systems for the purpose of regulating the discharge of ballast water as harmful to the marine environment for systems that kill aquatic organisms in ballast water by the administration of active substances such as sodium hypochlorite or ozone. You are setting approval criteria for. Therefore, in a system which treats ballast water by injecting an active substance into the ballast water, it is necessary to perform an evaluation test according to G9 (procedure regarding the approval of a ballast water management system using the active substance) to obtain approval. In addition, in the said approval standard, the substance produced | generated by administration of an active substance is also regulated as a related substance. For example, when the active substance is ozone, related substances produced by the reaction of bromine ions (Br ⁻ ) in ozone and seawater are bromoform (CHBr ₃ ), bromate ions (BrO ₃ ⁻ ), and residual oxidants. (Total Residual Oxidants: TRO).

TRO is a generic term for a substance that reacts with a neutral potassium iodide solution to release iodine and is an oxidizing substance similar to photochemical oxidant, ozone and the like.

The measurement of these oxidizing substances is conventionally performed, For example, there exist chemiluminescence method, an ultraviolet absorption method, the absorption photometry method, and the whole quantity method as a continuous measurement method of ozone concentration which causes air pollution.

On the other hand, the KI method which measures the reaction product based on reaction of potassium iodide and an oxidant is used as a measuring method of TRO concentration in ballast water (for example, patent document 4, 5). The measuring principle of this KI method will be described with an example of measuring ozone. First, iodine (I ₂ ) is liberated by the reaction of neutral potassium iodide and ozone. The reaction scheme is represented by the formula (1).

[Formula 1]

And the amount of iodine liberated is measured based on titration or the absorbance of wavelength 365nm, and ozone concentration is computed.

In addition, the residual chlorine concentration meter which measures residual chlorine which is one of TRO may use the DPD (diethyl-p-phenylenediammonium) absorption photometry (for example, JIS K0102 33.2) and a polarographic method. The residual chlorine concentration meter is used for monitoring the chlorine injected into the drainage for sterilization, and is an indispensable instrument for discharging the chlorine after discharging the treated water even in sewage treatment. Since sewage and drainage generally contain a large amount of bound residual chlorine, an oil reagent method is used.

The DPD absorbance photometric method, which is one of the reagents, measures the absorbance at wavelength 510 nm to 555 nm from the color of the residual red chlorine by the reaction caused by the reaction with the DPD reagent. Find the residual chlorine concentration. Only free residual chlorine is quantified by reaction with the DPD reagent. In addition, the addition of potassium iodide results in the development of bound residual chlorine, and the free residual chlorine and the combined residual chlorine can be quantitatively determined by measuring the absorbance (absorbance around wavelengths of 510 nm to 555 nm). Bonded residual chlorine can be calculated | required by subtracting free residual chlorine from this total value. In this DPD absorbance photometric method, oxidizing substances such as bromine, chlorine dioxide, permanganic acid and ozone are added to the measured value as positive errors.

On the other hand, in the measurement of the constant free residual chlorine, the polarography method which can perform on-line automatic measurement in many cases is used.

Japanese Patent Application Publication No. 2009-112978 Japanese Patent Application Publication No. 2006-314902 Japanese Patent Application Publication No. 2007-527798 Japanese Patent Application Laid-open No. Hei 9-248580 Japanese Patent Application Laid-open No. Hei 4-90892

Yukihiko Okamoto, et al., “Practical Use of Ship's Ballast Water Treatment System”, JFE Kibo, No. 25, February 2010, p. 1-6 Shuji Ueki, et al., “Development of Ballast Water Treatment System Using Ozone”, Mitsui Shipbuilding Kibo, No. 196, February 2009, p. 1-10

However, the free residual chlorine system by the polarographic method had the characteristic that a measured value becomes unstable from the difference of the electrical conductivity of sample water, or the density | concentration of another reducing substance, even if free residual chlorine concentration is the same. Therefore, it was difficult to apply the polarographic method to the control of the ballast water treatment system which has the factor which makes a measured value unstable.

In addition, the KI method requires about 10 minutes for reaction time for coloration (for example, Patent Document 4), and is employed as a measurement method for continuously monitoring the water quality of ballast water because of lack of rapidity. It didn't work.

Therefore, an object of this invention is to provide the measuring apparatus of TRO density | concentration which can measure TRO density | concentration promptly and has the measurement precision which can be used for control of a ballast water treatment system. Moreover, it aims at providing the method and monitoring system which monitor the TRO density | concentration of ballast water so that the ballast water discharged | emitted from a ballast water treatment system may satisfy | fill a standard using this TRO concentration measuring apparatus.

The measuring device of the residual oxidant concentration of the present invention which solves the above-mentioned problem is injected into a ballast water taken into a vessel by injecting an indicator reagent that reacts with the residual oxidant in the ballast water, and based on the absorbance of the colored indicator reagent. The residual oxidant concentration in the ballast water is measured.

Moreover, the measuring device of the residual oxidant density | concentration of this invention which solves the said subject is a form whose said indication reagent is N, N-diethyl-p-phenylenediamine salt in the measuring device of the residual oxidant concentration. have.

Moreover, the monitoring method of the residual oxidant density | concentration in the ballast water of this invention which solves the said subject is inject | poured into the ballast water taken into a ship, the indication reagent which reacts and colors with the residual oxidant in this ballast water, and said colored instruction | indication A method for monitoring residual oxidant concentration in the ballast water by a residual oxidant measuring device that measures the residual oxidant concentration in the ballast water based on the absorbance of a reagent, wherein the measuring device is discharged when the ballast water is discharged. The residual oxidant concentration in a ballast water is measured, and it is characterized by monitoring that this measured residual oxidant concentration is below a predetermined set value.

Moreover, the monitoring method of the residual oxidant concentration in the ballast water of this invention which solves the said subject is a monitoring method of the residual oxidant concentration in the said ballast water WHEREIN: When the said ballast water is taken in, the said measuring apparatus in the said ballast water The residual oxidant produced by the reaction of the active material for killing aquatic organisms with the ballast water is measured, and the amount of active substance injected into the ballast water is controlled based on the measured value of the residual oxidant. .

Moreover, the monitoring method of the residual oxidant concentration in the ballast water of this invention which solves the said subject measures the residual oxidant concentration in the ballast water which the said measuring apparatus discharges in the monitoring method of the residual oxidant concentration in the said ballast water, Based on this measurement result, the injection amount of the neutralizing agent which neutralizes the said residual oxidant is controlled, It is characterized by the above-mentioned.

Moreover, the monitoring method of the residual oxidant density | concentration in the ballast water of this invention which solves the said subject is the method of monitoring the residual oxidant density | concentration in the said ballast water WHEREIN: The residual oxidant concentration measured by the said measuring apparatus was more than the said set value. In this case, a treatment for removing the residual oxidant from the ballast water is performed.

The residual oxidant concentration measuring apparatus of the present invention which solves the above-mentioned problems is a measuring apparatus of residual oxidant concentration which measures the residual oxidant concentration in the said ballast water, in order to control the discharge process of the ballast water in a ship, The said ballast The indicator reagent containing N, N-diethyl-p-phenylenediamine salt was injected into the water, and the indicator reagent reacted with the remaining oxidant in the ballast water without injecting potassium iodide into the ballast water to color the indicator reagent. The residual oxidant concentration in the ballast water is measured based on the absorbance.

Moreover, the monitoring method of the residual oxidant density | concentration in the ballast water of this invention which solves the said subject measures the residual oxidant density | concentration in the ballast water discharged | emitted from the said vessel by the said measuring device of the residual oxidant density | concentration, and this measured residual oxidant density | concentration Is monitored to be equal to or less than a predetermined set value.

Moreover, the monitoring system of residual oxidant concentration in the ballast water of this invention which solves the said subject injects the indicator reagent containing N, N-diethyl- p-phenylenediamine salt into the ballast water discharged | emitted from a ship, Residual oxidant concentration measuring means for measuring the residual oxidant concentration in the ballast water based on the absorbance of the indicator reagent colored by reacting with the residual oxidant in the ballast water without injecting potassium iodide into the ballast water, and the residual oxidant And monitoring means for monitoring that the residual oxidant concentration measured by the concentration measuring means is equal to or less than a predetermined set value.

According to the above invention, the measuring apparatus of TRO density | concentration which can measure the residual oxidant (TRO) concentration in ballast water quickly can be obtained. In this TRO concentration measuring apparatus, the TRO concentration of the ballast water treatment system can be monitored. In addition, the residual oxidant (TRO) concentration in the ballast water can be measured, and the TRO concentration of the ballast water treatment system can be monitored.

1 is a schematic configuration diagram of a TRO concentration measuring device according to an embodiment of the present invention.
2 is a correlation diagram between a TRO measurement value of a TRO concentration measuring device according to an embodiment of the present invention and a TRO measurement value by the KI method.
3 is a configuration diagram of a ballast water treatment system according to Embodiment 1 of the present invention.
4 is a configuration diagram of a ballast water treatment system according to a second embodiment of the present invention.

An apparatus for measuring residual oxidant (TRO) concentration (hereinafter referred to as a TRO monitor) according to an embodiment of the present invention rapidly measures TRO in ballast water by DPD (diethyl-p-phenylenediamine) absorption photometry, Moreover, TRO is measured with the accuracy equivalent to or more than the conventional TRO concentration measuring method by the KI method.

In the TRO monitor according to the embodiment of the present invention, a DPD reagent is added to the water to be measured, and the absorbance (for example, absorbance at wavelength 510 nm to 550 nm) generated by the reaction between the DPD reagent and TRO is measured. By measuring the TRO concentration of the water under measurement.

Moreover, the TRO density | concentration monitoring method in ballast water by the TRO monitor concerning embodiment of this invention monitors the TRO density | concentration in ballast water by measuring the TRO density | concentration in ballast water with the TRO monitor which concerns on this invention.

As shown in FIG. 1, the TRO monitor 1 which concerns on embodiment of this invention is comprised from the measuring cell 2, the light source 3, the photodetector 4, and the control part 5. As shown in FIG.

The ballast water is sampled in the measurement cell 2, and DPD reagent is inject | poured into this sampled ballast water.

The light source 3 should just be able to irradiate the light containing the wavelength which the substance produced | generated by reaction of DPD reagent and TRO absorbs, and what is necessary is just to use a known light source, such as LED.

The photodetector 4 detects the intensity of light emitted from the light source 3 and transmitted through the cell.

The control part 5 measures the change of the absorbance in a cell by the absorption photometry on the basis of the intensity of the light detected by the photodetector 4.

The measurement procedure of TRO by the TRO monitor 1 which consists of the said structure is demonstrated. First, the ballast water is introduced into the measurement cell 2. A ballast water collects a fixed amount from the ballast water of the place to measure. At this time, the measurement cell 2 is washed by repeating the introduction and discharge of the ballast water into the measurement cell 2 a plurality of times. This sample collection may serve as the washing | cleaning of the measurement cell 2 by an overflow system. As a blank of the TRO monitor 1, light is irradiated from the light source 3 to the measuring cell 2 into which the ballast water is injected, and the intensity of the light transmitted through the measuring cell 2 is detected by the photodetector 4.

Next, DPD reagent and buffer are injected from the reagent reservoir 6 into the introduced ballast water.

The buffer serves to maintain the sample at an appropriate pH. For example, the pH of the sample may be adjusted to 6.3 to 6.6 using a phosphate buffer solution. As the DPD reagent, one commercially available as N, N-diethyl-p-phenylenediamine salt (for example, sulfate) was used. As the DPD reagent reacts with TRO in the ballast water, the sample develops in accordance with the concentration of TRO. In addition, the injection amount of a specific DPD reagent is set based on the DPD absorption photometry (JIS K0102 33.2) prescribed | regulated by JIS, for example.

After the injection of the DPD reagent, after a predetermined time (for example, within 2 minutes), light is irradiated from the light source 3 to the measurement cell 2, and the transmitted light intensity is detected by the photodetector 4. The absorbance is calculated based on the difference between the transmitted light intensity and the transmitted light intensity of the blank. By preparing a calibration curve of the TRO concentration in the sample and the absorbance at the TRO concentration in advance, the TRO concentration is calculated based on the detected absorbance.

As shown in Fig. 2, there is a correlation between the TRO measured value by the DPD absorbance photometric method and the TRO measured value by the KI method, and the measurement accuracy of the TRO concentration by the DPD absorbance photometric method contributes to the control of ballast water treatment as a TRO monitor. It can be seen that the measurement accuracy is possible. As shown in Fig. 2, the measured value of the TRO concentration measured after a predetermined time elapses after the injection of the DPD reagent and the measured value of the TRO concentration by the KI method are different. It is considered that this difference is because the KI method allows the measurement of stable oxidizing substances.

By the above operation, the TRO monitor 1 can measure the TRO concentration in the ballast water based on the absorbance of the ballast water to which the DPD reagent is added. Measurement of TRO concentration by this DPD absorbance photometric method is performed quickly (for example, within 1 minute), and since the TRO concentration measurement accuracy is equal to or higher than that of the conventional measuring method, as a TRO monitor that monitors the TRO concentration in the ballast water. It can contribute to the control of the ballast water treatment system. By repeating the measurement operation of the TRO concentration (for example, every 2.5 minutes), the TRO concentration in the ballast water can be monitored.

≪ Embodiment 1 >

The TRO monitor 1 which concerns on this invention can measure TRO in ballast water quickly and with high precision. Therefore, as the TRO monitor of the ballast water treatment system, the TRO concentration in the ballast water can be monitored.

The ballast water treatment system according to the first embodiment provided with the TRO monitor 1 according to the present invention will be described by illustrating a ballast water treatment system using sodium hypochlorite as an active substance. In addition, an active substance is not limited to this embodiment, You may use known active substances, such as chlorine, chlorine dioxide, and hydrogen peroxide.

When sodium hypochlorite is used as the active substance, related substances such as free residual chlorine and bonded residual chlorine are generated by the reaction of sodium hypochlorite and ballast water. Free residual chlorine is chlorine (Cl ₂ ), hypochlorite ions (ClO ⁻ ), etc., and has a strong bactericidal power and has an effect of killing aquatic organisms in ballast water. In addition, the bonding residual chlorine is a substance in which chlorine and ammonia are bonded, such as monochloramine (NH ₂ Cl) and dichloramine (NHCl ₂ ).

Here, the outline | summary of the conventional water quality monitor is demonstrated. Related substances, such as the above-mentioned free residual chlorine and bonded residual chlorine, remain in water as TRO. The concentration of this TRO was monitored by a measuring instrument having a specific function. These measuring instruments measured the respective TRO concentrations by a residual chlorine system, a redox potential meter, or a combination thereof capable of measuring the concentration and strength of the oxidizing substance contained in water.

Specifically, in the method of using sodium hypochlorite as the active substance, the ballast water into which sodium hypochlorite is injected so that the free residual chlorine concentration is required to kill the aquatic organisms in the ballast water at the time of intake of the ballast water. The free residual chlorine concentration in the solution is measured, and the amount of sodium hypochlorite injected is controlled based on this measured value. In addition, at the time of discharge of ballast water, the free residual chlorine in a ballast water is measured before discharge, and the injection amount of the chemical agent for neutralizing free residual chlorine is controlled according to this measured value. In addition, the concentration of TRO in the ballast water after the neutralizer was injected is measured to confirm whether the discharged ballast water satisfies the discharge standard.

The TRO monitor 1 according to the present invention quickly monitors the TRO concentration in the ballast water by adding a DPD reagent and measuring the TRO concentration. The TRO monitor 1 monitors the TRO concentration of the ballast water at the time of intake and discharge of the ballast water of a system in which the ballast water is treated using sodium hypochlorite. That is, at the time of intake of ballast water, the injection amount of the active substance injected into the ballast water is controlled based on the measured value of the TRO concentration in the ballast water after the active substance injection. When the ballast water is discharged, the injection amount of the neutralizing agent that neutralizes the remaining amount of the injected active substance is controlled based on the measured value of the TRO concentration in the ballast water. Moreover, based on the measured value of TRO density | concentration in ballast water after injection of a neutralizing agent, it is confirmed whether the ballast water discharged | emitted satisfy | fills discharge standard.

As shown in FIG. 3, the ballast water treatment system 7 according to the first embodiment of the present invention includes a ballast tank 8, an active substance injection unit 9, a neutralizer injection unit 10, and a TRO monitor 1. ) And a chemical quantity control unit 11.

The ballast tank 8 stores ballast water which prevents the hull from rising during navigation in the course of a ship with little dripping.

The active substance injection part 9 is connected to the ballast tank 8 via the pump 12, and injects sodium hypochlorite into the ballast water conveyed to the ballast tank 8.

The neutralizing agent injection part 10 is provided downstream of the ballast tank 8, and injects the neutralizing agent for removing related substances, etc. in ballast water. Examples of the neutralizing agent include sodium thiosulfate, ascorbic acid, oxalic acid, sodium sulfite, sodium bisulfite and the like.

The TRO monitor 1 measures the TRO concentration in the ballast water produced by the reaction of the injected sodium hypochlorite and seawater.

The chemical quantity control unit 11 receives the measurement data of the TRO monitor 1, transmits a control signal for controlling the injection amount of the active substance to the active substance injection unit 9, and the neutralizing agent injection unit 10. Send a control signal to control the injection amount of the neutralizer.

The operation of the ballast water treatment system 7 according to the first embodiment of the present invention having the above configuration will be described.

At the time of intake of the ballast water, the pump 12 is driven, and the seawater or fresh water is transferred to the ballast tank 8 through the filter 13 and the active substance injection unit 9. At this time, in the active substance injection section 9, sodium hypochlorite is injected into the ballast water at a predetermined injection rate in accordance with the flow rate of the ballast water passing through the active substance injection section 9. Moreover, sea water or fresh water may be transferred to the ballast tank 8 by the head difference without providing the pump 12.

The TRO monitor 1 measures the TRO concentration of the ballast water in which sodium hypochlorite is injected, and transmits the measurement result to the chemical quantity control unit 11. The chemical quantity control unit 11 transmits a control signal to the active substance injecting unit 9 based on this measurement result, and the sodium hypochlorite injected into the ballast water so that the measured value of the TRO concentration becomes a predetermined target value. Control the injection volume. In this way, by maintaining the concentration of TRO in the ballast water above a certain level, it is possible to prevent regrowth of aquatic organisms and hatching such as plankton while the ballast water is stored in the ballast tank 8.

On the other hand, in discharging the ballast water, the ballast water stored in the ballast tank 8 is discharged out of the ship through the neutralizer injection unit 10 by driving the pump 14. At this time, the TRO monitor 1 measures the concentration of TRO in the ballast water before the neutralizing agent is injected, and transmits this measurement result to the chemical quantity control unit 11. Based on the measured value of the TRO monitor 1, the chemical amount control unit 11 calculates the injection rate of the neutralizing agent required for the ballast water after the neutralizing agent is injected into a reduced state (that is, a state in which TRO is not detected). Then, the chemical amount control unit 11 controls the neutralizing agent injection unit 10 based on the injection rate of the neutralizing agent, the neutralizing agent is injected into the ballast water, and the related substances in the ballast water are removed.

In addition, the TRO monitor 1 measures the TRO concentration of the ballast water after the neutralizer injection, and when the TRO concentration of a predetermined level or more is measured in the ballast water after the neutralizer injection, the chemical quantity control unit 11 performs the injection operation of the neutralizer. The pump 14 for discharging the ballast water is stopped.

Thereby, neutralization of the relevant substance in ballast water is inadequate, and the discharge operation | movement of ballast water which does not satisfy a drainage standard can be stopped reliably.

As described above, according to the ballast water treatment system 7 according to the first embodiment, at the time of intake of the ballast water, the TRO monitor 1 measures the TRO concentration, and the amount of sodium hypochlorite injected into the ballast water is aquatic. The need for killing can also be controlled to avoid excess. In addition, at the time of ballast water discharge, the TRO concentration is measured by the TRO monitor 1, so that the neutralizing agent for neutralizing the free residual chlorine can be controlled so as not to be excessive. In addition, the TRO monitor 1 can monitor the water quality of the ballast drainage by measuring the TRO concentration after the neutralizer injection. In the ballast water treatment, the ballast water intake process and the ballast water discharge process are not performed at the same time. Therefore, even if one TRO monitor 1 measures the TRO concentration of the ballast water intake process and the discharge process, It does not interfere.

And since the TRO monitor 1 which concerns on this invention can measure TRO in ballast water quickly and with high precision, by applying this TRO monitor 1 to a ballast water treatment system, in the ballast water treatment process, The dosage of active substance and neutralizer can be minimized. Therefore, it is possible to suppress the amount of the active substance and the neutralizing agent loaded on the ship. In addition, the number of TRO monitors for measuring TRO concentration can be reduced by measuring the water quality at the time of intake of the ballast water and at the time of discharge of the ballast water, using a single TRO monitor (1). Savings can be realized.

In addition, the ballast water treatment system 7 according to Embodiment 1 can remove related substances by inject | pouring into the ballast water the neutralizing agent which neutralizes the relevant substance, without using an adsorbent. That is, according to this system, although the necessity of replenishment and storage of a neutralizing agent is required with an active substance, the installation space of an adsorption installation is unnecessary, and the cost of regular replacement of the adsorbent accompanying installation of an adsorption installation is reduced.

≪ Embodiment 2 >

The TRO monitor 1 which concerns on this invention can measure TRO in ballast water quickly and with high precision. Therefore, as the TRO monitor 1 of the ballast water treatment system, the TRO concentration in the ballast water can be monitored.

The ballast water treatment system according to the second embodiment provided with the TRO monitor 1 according to the present invention will be described by illustrating a ballast water treatment system using ozone as an active substance. In addition, an active substance is not limited to this Example, You may use a known active substance.

When ozone is used as the active substance, related substances such as bromate ions, bromoform and TRO are produced by the reaction of ozone and bromine ions in seawater. If the ballast water is discharged with the toxicity of the related material remaining in the ballast water at the time of discharge, it causes a second environmental pollution, so it is necessary to remove the related material in the discharged ballast water.

Therefore, in the related art, a discharge treatment tank filled with an adsorbent is provided in the discharge path of the ballast water, and the related material of the ballast water is removed at the time of discharge of the ballast water. Although this adsorbent is excellent in the removal ability, such as adsorption to a related substance etc., there is a limit to the ability. As for the adsorption capacity, if water flow is continued, the adsorption layer filled with the adsorbent gradually becomes saturated, and eventually breaks through and the adsorption capacity is lost. That is, it is impossible to remove adsorption above the saturated adsorption amount of the adsorbent filled in the discharge treatment tank.

Therefore, in order to ensure the monitoring of the related substance removal performance in a waste disposal tank, the TRO monitor always monitored the quality of the ballast water after passing through the waste disposal tank.

In this method, when the measured value of the TRO monitor does not satisfy the emission standard, it is impossible to drain the ballast water into the sea in the usual procedure, and as a result, there is a possibility that a problem such as delayed loading of the dropping may occur. . In order to prevent such a situation, it is necessary to separately prepare a preliminary adsorption apparatus and to remove the related substance in ballast discharge. However, if a preliminary adsorption device is prepared, an extra space for storing this adsorbent is required.

As shown in FIG. 4, the ballast water treatment system 15 according to the second embodiment of the present invention includes a ballast tank 8, an ozone injection unit 16, an exhaust treatment unit 17, a TRO monitor 1, And a discharge control unit 18.

The ballast tank 8 stores ballast water which prevents the hull from rising during navigation in the course of a ship with little dripping.

The ballast tank 8 is connected to the ozone injection unit 16 via a pump 12 for taking in the ballast water, and ozone is injected into the ballast water delivered to the ballast tank 8.

The discharge processing part 17 is connected to the ballast tank 8 via the pump 19 which discharges ballast water out of a ship, and the valve 20 which controls the flow path of ballast water. This valve 20 is controlled by the discharge control part 18 mentioned later. The valve 20 is connected to a pipe 21 for discharging the ballast water out of the vessel without passing through the discharge treatment unit 17.

The TRO monitor 1 measures the concentration of TRO in the ballast water before and after the treatment of the discharge treatment unit 17 at the time of discharge of the ballast water. The TRO monitor 1 samples the ballast water of the inlet and the outlet of the discharge processing unit 17 at different times, respectively, and measures the concentration of TRO in the sampled ballast water. This measurement data is transmitted to the discharge control part 18 mentioned later.

The discharge control part 18 inputs the measured value of the TRO monitor 1, and controls the pump 19 and the valve 20 based on this measured value.

The operation of the ballast water treatment system 15 according to the second embodiment of the present invention having the above configuration will be described.

At the time of intake of the ballast water, the pump 12 is driven to transfer the seawater or fresh water to the ballast tank 8 through the filter 13 and the ozone injection unit 16. In addition, the ballast water may be introduced into the ballast tank 8 using the head difference without providing the pump 12.

In the ozone injection unit 16, a predetermined amount of ozone is injected into the ballast water so that the ozone concentration in the ballast water becomes a concentration necessary for killing aquatic organisms, depending on the flow rate of the ballast water passing through the ozone injection unit 16. . The ballast water into which ozone is injected is stored in the ballast tank 8. In addition, the piping upstream of the ballast tank 8 is provided with the degassing process part not shown in figure, and excess ozone is removed from ballast water in this degassing part. As described above, since ozone is degassed from the ballast water, and the ozone remaining in the ballast water is a substance that is easily decomposed, there is little ozone in the ballast water transferred to the ballast tank 8.

On the other hand, in discharging the ballast water, the ballast water stored in the ballast tank 8 by driving the pump 19 is transferred out of the ship through the discharge treatment unit 17. At this time, the TRO monitor 1 measures the concentration of TRO in the ballast water before and after the treatment by the discharge treatment unit 17, and the measurement result is transmitted to the discharge control unit 18. The TRO concentration measurement of the ballast water before and after the treatment by the TRO monitor 1 includes a procedure for sampling the ballast water before the treatment by the wastewater treatment unit 17 and a ballast water after the treatment with the wastewater treatment unit 17. This can be done by switching the procedure every fixed time.

The exhaust treatment unit 17 removes related substances (bromoform, residual oxidant, etc.) in the ballast water by chemical reaction, adsorption, or the like. As the adsorbent to be filled in the discharge treatment unit 17, known adsorbents such as coal activated carbon, palm husk activated carbon, zeolite, ceramic, and the like are exemplified. In addition, you may use the shape of an adsorption material of any shape, such as a granular form, a powder form, and a fibrous form.

As an example, the discharge processing part 17 which filled 2 m <3> of palm husk activated carbon was arrange | positioned downstream of the ballast tank 8, and the test object in which ozone was inject | poured so that it may become 4 mg / l with respect to a process flow volume 200m <3> / An experiment was carried out to distribute to the discharge treatment unit 17 at h. This experiment confirmed that the performance of removing related substances (mainly TRO) in the ballast water passing through the discharge treatment tank 17 sufficiently satisfies the performance for a long time. In G9, since the behavior of related substances is strictly checked, the ballast water is treated by the discharge treatment unit 17 so as not to cause the second environmental pollution.

The discharge control unit 18 controls the processing route of the ballast water based on the measured value of the TRO monitor 1. That is, when the TRO concentration on the inlet side of the discharge processing unit 17 is equal to or less than a preset value (for example, 0.15 mg / l, etc.), the discharge control unit 18 controls the valve 20, so that the ballast water It is discharged out of the ship through the pipe (21). That is, the ballast water is discharged out of the ship without passing through the discharge treatment unit 17. Therefore, it is possible to prevent the consumption of the adsorbent filled in the discharge treatment unit 17.

On the other hand, when the concentration of TRO on the inlet side of the discharge processing unit 17 is equal to or greater than a preset value (for example, 0.15 mg / l, etc.), the discharge control unit 18 controls the valve 20 to control the ballast water. It transfers to the discharge processing part 17. Therefore, the ballast water can be discharged out of the ship by treating the ballast water in the discharge treatment unit 17 and removing related substances in the ballast water, which is suitable for the ship ballast water management treaty adopted by the IMO. At this time, the TRO concentration after passing through the discharge treatment unit 17 is measured by the TRO monitor 1, and it can be confirmed that the TRO concentration in the ballast water is equal to or less than a preset value (for example, 0.15 mg / l or the like). .

If the TRO concentration in the ballast water is equal to or higher than a predetermined value, the pump 19 stops the discharge operation of the ballast water that does not satisfy the drainage standard.

As described above, according to the ballast water treatment system 15 according to the second embodiment, the concentration of TRO in the ballast water before being introduced into the discharge treatment unit 17 is measured, and the ballast water is discharged based on the measurement result. Can be controlled.

According to the TRO monitor 1 according to the present invention, the TRO concentration in the ballast water can be measured quickly and with high accuracy. By using this TRO monitor 1, by controlling the treatment route of the wastewater treatment, it is possible to optimize the loading amount of the adsorbent to be filled in the discharge treatment unit 17 and to increase the lifetime of the adsorbent.

In addition, the method of monitoring the TRO density | concentration in the ballast water by the TRO monitor 1 and TRO monitor 1 concerning this invention is not limited to the said embodiment, In the range which does not impair the effect of this invention. You can change the settings accordingly. For example, the indicating reagent is not limited to DPD, and can be applied to the present invention as long as it reacts rapidly with TRO in the ballast water and exhibits a color reaction.

As described above, according to the TRO monitor 1 of the present invention, the TRO concentration in the ballast water can be measured quickly and with high accuracy. Moreover, the TRO monitor of this invention can measure TRO which is toxic in an organism with high precision, without measuring other stable oxidizing substance like the measurement of TRO concentration by the KI method. Therefore, it is possible to monitor whether or not the TRO concentration in the ballast water satisfies the discharge standard at the time of draining the ballast water. In addition, when neutralizing TRO in ballast water, the injection amount of the neutralizing agent which neutralizes TRO can be suppressed so that it may become necessary and sufficient. In addition, even when the TRO removal operation is performed, the TRO which is toxic to living organisms can be measured with high accuracy, so that an excessive removal operation can be prevented.

And since the TRO monitor of this invention can monitor the TRO density | concentration of ballast water, it can be used for control of a ballast water treatment system. Moreover, the TRO monitor of this invention can monitor the TRO density | concentration of the process water of several places with one TRO monitor in the system of ballast water treatment. Therefore, the number of TRO monitors used in the ballast water treatment system can be reduced, and space saving of the ballast water treatment system is realized.

1: TRO monitor (measuring device of residual oxidant concentration)
2: measuring cell
3: light source
4: light detector
7: ballast water treatment system
8: ballast tank
9: active material injection unit
10: neutralizer injection unit
11: chemical amount control unit
9, 12, 14: Pump
15: ballast water treatment system
16: ozone injection unit
17: discharge treatment unit
18: discharge control unit
20: valve

Claims (15)

An indicator reagent containing N, N-diethyl-p-phenylenediamine salt was injected into the ballast water withdrawn from the ship, and the reaction was performed based on the absorbance of the indicator reagent colored by reacting with the remaining oxidant in the ballast water. It is a monitoring method of the residual oxidant concentration in the said ballast water by the residual oxidant measuring apparatus which measures the residual oxidant concentration in ballast water,
At the time of intake of the ballast water, the measuring device injects the indicator reagent into the ballast water into which sodium hypochlorite for killing aquatic organisms in the ballast water and reacts with the remaining oxidant in the ballast water to color. Measure the residual oxidant concentration in the ballast water based on the absorbance of the indicator reagent, and control the injection amount of the sodium hypochlorite injected into the ballast water based on the measured value of the residual oxidant concentration,
At the time of discharging the ballast water, the measuring device injects the indicator reagent into the discharged ballast water, and the residual oxidant in the ballast water based on the absorbance of the indicator reagent colored by reacting with the residual oxidant in the ballast water. The method of monitoring the residual oxidant concentration in ballast water characterized by measuring a density | concentration and monitoring that this measured residual oxidant concentration is below a predetermined set value. The method of claim 1,
The measuring device injects the indicator reagent into the ballast water before the neutralizing agent neutralizing the residual oxidant in the ballast water is injected, and reacts with the residual oxidant in the ballast water based on the absorbance of the indicator reagent. The residual oxidant concentration in water is measured, and the injection amount of the said neutralizing agent is controlled based on the measured value of this residual oxidant concentration, The monitoring method of the residual oxidant concentration in ballast water. In a ballast water treatment system for injecting ozone into ballast water taken into a vessel and killing aquatic organisms in the ballast water, residual oxidants in ballast water for monitoring residual oxidants generated by the reaction of the ballast water and the ozone. Concentration monitoring method,
Injecting an indicator reagent containing N, N-diethyl-p-phenylenediamine salt into the ballast water discharged from the ballast water treatment system, and reacting with the residual oxidant in the ballast water to absorb the color of the indicator reagent. Based on the residual oxidant concentration in the discharged ballast water, and monitoring that the measured residual oxidant concentration is below a predetermined set value,
And a process for removing the residual oxidant from the ballast water when the residual oxidant concentration in the discharged ballast water is equal to or greater than the set value. A measuring cell into which a ballast water taken into a vessel is introduced, an indicating reagent injecting an indicator reagent containing N, N-diethyl-p-phenylenediamine salt into the measuring cell into which the ballast water is introduced, and the indicating reagent The light source which irradiates this injected ballast water with the wavelength of 510 nm-550 nm, the photodetector which detects the light which permeate | transmitted the said measuring cell, and the remainder in the said ballast water based on the detection result of the said photodetector A method for monitoring residual oxidant concentration in ballast water by a residual oxidant concentration measuring device having a control unit that calculates the absorbance of the indicated reagent reacted with an oxidant and calculates the residual oxidant concentration in the ballast water based on the absorbance. ,
The residual oxidant concentration in the ballast water after injection of an active substance of any one of sodium hypochlorite, chlorine, chlorine dioxide, and hydrogen peroxide for killing aquatic organisms in the ballast water and a neutralizing agent for neutralizing the active substance is injected. The residual oxidant concentration measuring device is measured,
The monitoring method of the residual oxidant concentration in ballast water characterized by monitoring that this measured residual oxidant concentration is below a predetermined set value. A ballast tank for storing ballast water withdrawn from the vessel,
An active substance injecting unit for injecting an active substance of any one of sodium hypochlorite, chlorine, chlorine dioxide, and hydrogen peroxide for killing aquatic organisms in the ballast water into the ballast water introduced into the ballast tank;
A neutralizing agent injecting unit for injecting a neutralizing agent for neutralizing the active substance;
A residual amount of oxidant monitoring system for monitoring the residual oxidant concentration of the ballast water treatment system having a chemical amount control unit for controlling the injection amount of the drug injected from the active substance injection unit and the neutralizer injection unit,
A measurement cell into which the ballast water into which the neutralizing agent is introduced is introduced, an indicator reagent injection means for injecting an indicator reagent containing N, N-diethyl-p-phenylenediamine salt into the measurement cell into which the ballast water is introduced, and the indication A light source for irradiating light with a wavelength of 510 nm to 550 nm to the ballast water injected with a reagent, a photodetector for detecting light passing through the measuring cell, and a detection result of the photodetector in the ballast water. Residual oxidant concentration measuring means having a control unit for calculating the absorbance of the indicator reagent colored by reacting with the residual oxidant and calculating the residual oxidant concentration in the ballast water based on the absorbance;
And a monitoring means for monitoring that the residual oxidant concentration measured by said residual oxidant concentration measuring means is equal to or less than a predetermined set value. The method of claim 5,
When injecting ballast water into the vessel, ballast water into which the active substance is injected is introduced into the measuring cell,
The residual oxidant concentration measuring means injects the indicator reagent into the ballast water into which the active substance is injected, and the residual oxidant concentration in the ballast water based on the absorbance of the indicator reagent colored by reacting with the residual oxidant in the ballast water. Is measured,
And said chemical amount control means controls the injection amount of said active substance injected into said ballast water based on the measured value of said measured residual oxidant concentration. The method according to claim 5 or 6,
When discharging ballast water from the vessel, the ballast water before the neutralizing agent is introduced into the measuring cell is further introduced,
The residual oxidant concentration measuring means injects the indicator reagent into the ballast water before the neutralizing agent is injected, and the residual oxidant concentration in the ballast water based on the absorbance of the indicator reagent colored by reacting with the residual oxidant in the ballast water. Is measured,
The chemical amount control means controls the injection amount of the neutralizing agent based on the measured value of the measured residual oxidant concentration. A ballast tank for storing ballast water withdrawn from the vessel,
A residual oxidant concentration monitoring system for monitoring residual oxidant concentration of a ballast water treatment system, having an ozone injection unit for injecting ozone for killing aquatic organisms in the ballast water into ballast water introduced into the ballast tank;
A measurement cell into which a ballast water discharged from the ballast tank is introduced, an indicator reagent injection means for injecting an indicator reagent containing N, N-diethyl-p-phenylenediamine salt into the measurement cell into which the ballast water is introduced; A light source for irradiating light having a wavelength of 510 nm to 550 nm to the ballast water injected with an indicator reagent, a photodetector for detecting light passing through the measuring cell, and the ballast water based on a detection result of the photodetector Residual oxidant concentration measuring means having a control part which calculates the absorbance of the said indicated reagent reacted with the residual oxidant in water, and calculates the residual oxidant concentration in the ballast water based on the absorbance;
Monitoring means for monitoring that the residual oxidant concentration measured by the residual oxidant concentration measuring means is equal to or less than a predetermined set value;
When the residual oxidant concentration measured by the said residual oxidant concentration measuring means was more than the preset value, the residual oxidant removal means which performs the process which removes the said residual oxidant from the said ballast water is provided, It is characterized by the above-mentioned. Surveillance system. delete delete delete delete delete delete delete

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