JP6725712B1 - Water treatment method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To effectively suppress clogging of a granular material packed layer with bubbles caused by hydrogen peroxide while adopting an accelerated oxidation treatment step using both ozone and hydrogen peroxide, and to improve the bromate ion concentration. Provided is a water treatment method capable of obtaining sufficiently low treated water. SOLUTION: After the step (A) of subjecting the water to be treated to an accelerated oxidation treatment by a predetermined method, a step (B) of reacting hydrogen peroxide with a reducing agent for reduction treatment to decompose is carried out, and thereafter, It is a water treatment method of carrying out the step (C) of adsorbing the treated water through the granular material packed bed. [Selection diagram] Figure 1

Description

The present invention relates to a water treatment method. In particular, the present invention relates to a water treatment method in which treated water containing a bromine-containing component is subjected to oxidation treatment to obtain treated water.

Conventionally, by utilizing the characteristic that ozone has a strong oxidizing power, a wide range of water treatments have been carried out by oxidizing ozone gas into the water to be treated to oxidize and remove organic substances, inorganic substances, musty odor substances, etc. in the water to be treated. Has been implemented. In the ozone treatment, an oxidative decomposition reaction by ozone molecules and an oxidative decomposition reaction by hydroxy radicals generated by decomposition of ozone molecules are performed. In recent years, in particular, it has been found that the oxidative power of hydroxy radicals is very high. By combining ultraviolet rays and hydrogen peroxide with ozone, the generation of hydroxy radicals is promoted, and ozone molecules are decomposed. Attention has been focused on a water treatment method called an advanced oxidation process (AOP) that can decompose difficult-to-decompose substances.

In the accelerated oxidation treatment, when the water to be treated contains a bromine-containing component, this may react with ozone to generate bromate ions. Therefore, in order to decompose bromate ions generated by the accelerated oxidation treatment, a treatment method has been studied in which the water to be treated is subjected to the accelerated oxidation treatment and then the reducing agent treatment is performed (see, for example, Patent Document 1). Patent Document 1 describes that in the reducing agent treatment step, the water to be treated that has been subjected to the accelerated oxidation treatment is adjusted to have a pH of 5 or less and then brought into contact with the reducing agent.

JP, 2003-62583, A

However, the treatment method described in Patent Document 1 has room for reducing the concentration of bromate ions in the treated water obtained through the reducing agent treatment step.

Further, in the water treatment method adopting the accelerated oxidation treatment, for example, a packed bed (hereinafter, referred to as “particulate packed bed”) filled with activated carbon powder and other granular adsorbents after the accelerated oxidation treatment step. The process of introducing the water to be treated which has been subjected to the accelerated oxidation treatment process is generally carried out for. Here, when hydrogen peroxide is added for the purpose of accelerating the generation of hydroxy radicals in the accelerated oxidation treatment step, that hydrogen peroxide remains in the water to be treated introduced into the granular material packed bed. There is. Then, hydrogen peroxide may be decomposed and foamed in the granular material-filled layer, and voids in the granular material-filled layer may be filled with bubbles to block the granular material-filled layer.

Therefore, the present invention is a water treatment method that employs an accelerated oxidation treatment step in which ozone and hydrogen peroxide are used in combination, and effectively suppresses clogging of a granular material packed layer with bubbles caused by hydrogen peroxide. Meanwhile, it is an object of the present invention to provide a water treatment method capable of obtaining treated water having a sufficiently low bromate ion concentration.

The present inventor has made earnest studies for the purpose of solving the above problems. The present inventor performs an accelerated oxidation treatment step in which ozone and hydrogen peroxide are used in combination in a manner that makes it difficult to generate bromate ions, and reduces the water to be treated that has undergone the accelerated oxidation treatment step. By adding an agent to decompose the hydrogen peroxide remaining in the water to be treated that is not consumed in the accelerated oxidation treatment step and then supplying it to the granular material packed layer, the granular material packed layer is caused by hydrogen peroxide. The inventors have found that it is possible to obtain treated water having a sufficiently low bromate ion concentration while effectively suppressing clogging by bubbles that occur, and completed the present invention.

That is, the present invention is intended to advantageously solve the above problems, the water treatment method of the present invention is a water treatment to obtain a treated water by oxidizing the water to be treated containing a bromine-containing component A method of adding ozone and hydrogen peroxide to the water to be treated to accelerate the water to be treated (A); and the water to be treated after the step (A). On the other hand, a step (B) of decomposing hydrogen peroxide remaining in the treated water by adding a reducing agent to form a treated water-reducing agent mixture, and the treated water after the step (B) are granular. A step (C) of passing through a body-filled layer, and at least (i) setting the bromate ion concentration in the water to be treated after the step (A) to 15 μg/L or less, or (ii) The addition amount of the hydrogen peroxide added in the step (A) is at least twice the addition amount of the ozone on a molar basis. To do. According to such a water treatment method, it is possible to obtain treated water having a sufficiently low bromate ion concentration while effectively suppressing clogging of the granular material packed layer with bubbles caused by hydrogen peroxide.

Here, in the water treatment method of the present invention, the pH of the water to be treated-reducing agent mixture in the step (B) is preferably more than 5.0. This is because such a water treatment method can more effectively prevent the granular material-filled layer from being clogged with bubbles caused by hydrogen peroxide.

Further, in the water treatment method of the present invention, it is preferable that the reducing agent added in the step (B) is a sulfite. This is because such a water treatment method can more effectively prevent the granular material-filled layer from being clogged with bubbles caused by hydrogen peroxide.

Furthermore, in the water treatment method of the present invention, it is preferable that the oxidation-reduction potential of the water to be treated which has undergone the step (C) is higher than 0. This is because such a water treatment method can further improve the water treatment efficiency.

According to the water treatment method of the present invention, when adopting the accelerated oxidation treatment step in which ozone and hydrogen peroxide are used in combination, it is possible to effectively prevent the granular material packed layer from being clogged with bubbles caused by hydrogen peroxide. Meanwhile, it is possible to obtain water to be treated having a sufficiently low bromate ion concentration.

It is explanatory drawing which shows schematic structure of the typical water treatment apparatus which performs the water treatment method according to this invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The water treatment method of the present invention is not particularly limited, and can be used, for example, in a water treatment plant or the like for advanced treatment for removing organic substances, inorganic substances, odorous substances, etc. in water to be treated containing bromine-containing components. .. In addition, when the ozone treatment and the accelerated oxidation treatment are used in the sewage reclaimed water utilization process, which has been widely used in recent years, particularly when the reclaimed water is used in such a case that there is a high possibility that the person comes into direct contact, The present invention can be preferably applied from the viewpoint of improving the properties and the like.

(Water treatment method)
The water treatment method of the present invention is a water treatment method in which treated water containing a bromine-containing component is subjected to an oxidation treatment to obtain treated water, to the treated water, ozone and hydrogen peroxide are added, A step (A) in which the water to be treated is subjected to an accelerated oxidation treatment by a predetermined method, and a reducing agent is added to the water to be treated after the step (A) to be left in the water to be treated as a water-reducing agent mixture. The method is characterized by including a step (B) of decomposing the hydrogen peroxide and a step (C) of passing the water to be treated after the step (B) through the granular material packed bed. In the water treatment method of the present invention, after the step (A) of subjecting the water to be treated to an accelerated oxidation treatment by a predetermined method, a step (B) of reacting hydrogen peroxide with a reducing agent to reduce and decompose it is carried out. Then, by carrying out the step (C) of adsorbing the water to be treated through the granular material packed layer, it is possible to effectively prevent the granular material packed layer from being clogged by bubbles caused by hydrogen peroxide. It is possible to obtain treated water having a sufficiently low bromate ion concentration.

FIG. 1 shows a schematic configuration of an example of a typical water treatment apparatus that can be used to carry out the water treatment method according to the present invention. The water treatment device 100 includes the accelerated oxidation treatment tank 20 capable of performing the above-described step (A), the reduction treatment tank 30 capable of performing the step (B), and the adsorption treatment tank 40 capable of performing the step (C). Prepare The water treatment device 100 introduces water to be treated containing a bromine-containing component into the water treatment device 100 through an inlet (not shown) by gravity flow or by pumping water, and the water to be treated is treated in the accelerated oxidation treatment tank 20. After bringing the hydrogen peroxide and ozone into contact with each other, a predetermined treatment is further performed in the reduction treatment tank 30 and the adsorption treatment tank 40, and the resultant is discharged from the apparatus through a discharge port (not shown). In the following, in the water treatment device 100, the inlet side may be referred to as the “front stage side”, and the outlet side may be referred to as the “rear stage side”. Then, in the accelerated oxidation treatment tank 20, the accelerated oxidation treatment is performed in such a manner that bromate ions are less likely to be generated.

Preferably, the water treatment device 100 includes an ozone contact tank 10 in front of the accelerated oxidation treatment tank 20 and an ozone generator 50 that generates ozone to be supplied to the ozone contact tank 10 and the accelerated oxidation treatment tank 20. .. Further, the water treatment device 100 preferably includes a dissolved ozone concentration measuring device 61 capable of measuring the dissolved ozone concentration in the water to be treated which has passed through the ozone contact tank 10. Furthermore, the water treatment device 100 may optionally include a bromate ion concentration measuring device 62 capable of measuring the bromate ion concentration in the water to be treated that has undergone the step (C) on-site. In the following description, various steps included in the accelerated oxidation treatment method according to the present invention will be described as steps that occur in each constituent portion, but the water treatment method according to the present invention will not be affected by the presence or absence of any physical constituent portion. It is not limited. That is, for example, regardless of the presence or absence of a "water tank" in which the accelerated oxidation treatment may occur, if ozone and hydrogen peroxide are supplied to the water to be treated and a predetermined accelerated oxidation treatment is performed, the present invention It is included in the category of such accelerated oxidation treatment methods.

<Water to be treated>
The water to be treated that is the treatment target of the water treatment device 100 is not particularly limited, and examples thereof include raw water for tap water. Specifically, examples of the water to be treated include water taken from dams and rivers, lake water, well water, spring water, and groundwater. Further, the water to be treated contains a bromine-containing component and may further contain a substance to be decomposed such as an organic substance.

<Ozone contact tank>
The ozone contact tank 10, which is an optional component, performs the step (D) of bringing ozone into contact with the water to be treated. By performing the step (D) before the step (A), the decomposition of the decomposition target substance in the water to be treated can be promoted, and the accelerated oxidation treatment can be performed more effectively in the accelerated oxidation treatment tank 20. it can. The ozone contact tank 10 introduces ozone generated by an ozone generator 50, which will be described later, into the tank via a first ozone diffuser 51. The ozone contact tank 10 may be a commonly used general ozone contact tank. The contact between the water to be treated and ozone is performed by, for example, the ozone introduced into the tank as fine bubbles flowing in the water to be treated. At this time, in order to improve the contact efficiency between the water to be treated and ozone, stirring, miniaturization of bubbles, adjustment of ozone introduction rate, etc. can be appropriately performed. In this way, the ozone that has come into contact with the water to be treated partially reacts with the decomposition target substance in the water to be decomposed, and the rest is dissolved in the water to be treated.

<Promoted oxidation treatment tank>
Optionally, the water to be treated contacted with ozone in the ozone contact tank 10 is supplied to the accelerated oxidation treatment tank 20. In the accelerated oxidation treatment tank 20, the step (A) of performing the accelerated oxidation treatment of the water to be treated is carried out in a predetermined mode that makes it difficult to generate bromate ions. Specifically, in the water treatment method of the present invention, at least (i) the bromate ion concentration in the water to be treated after the step (A) is set to 15 μg/L or less, or (ii) on a molar basis, Either the amount of hydrogen peroxide added should be twice or more the amount of ozone added.

In the case of the above (i), there is no particular limitation on the specific method for setting the bromate ion concentration in the water to be treated after the step (A) to 15 μg/L or less. In carrying out the above (i), the addition amount of at least one of ozone and hydrogen peroxide may be adjusted in the step (A), or the amount of ozone and/or hydrogen peroxide may be adjusted before the step (A) or in the step (A). The step (A) may be carried out in a state where hypochlorite or ammonium salt is added to the treated water.

The bromate ion concentration in the water to be treated after the step (A) is preferably 15 μg/L or less, more preferably 10 μg/L or less. When the bromate ion concentration in the water to be treated after the step (A) is not more than the above upper limit value, the obtained water to be treated is further excellent in water quality. The bromate ion concentration in the water to be treated after the step (A) is not particularly limited and can be measured by a known general method. For example, the water treatment device 100 includes a water sampling pipe (not shown) in a pipe that connects the accelerated oxidation treatment tank 20 and the reduction treatment tank 30, and the water to be treated collected through the water sampling pipe is subjected to ion chromatography. -The bromate ion concentration in the water to be treated can be measured by analyzing according to the post-column method.

Further, in the case of the above (ii), at least one of the addition amount of hydrogen peroxide and the addition amount of ozone in step (A) is adjusted so that the addition amount of hydrogen peroxide is the addition amount of ozone. Be more than twice the amount. Here, the addition amount of hydrogen peroxide in the step (A) is preferably 5 times or more, and more preferably 10 times or more, of the addition amount of ozone on a molar basis. This is because the generation of bromate ions can be suppressed even better. The addition ratio in the step (A) can be usually 15 times or less.

In addition, as described in (ii) above, that is, a means for making the bromate ion concentration in the water to be treated after step (A) to be 15 μg/L or less is as described in (ii) above. In step (A), the amount of hydrogen peroxide added may be twice or more the amount of ozone added on a molar basis. In other words, in step (A), both (i) and (ii) above may be satisfied. Further, even in the case where the step (D) of bringing ozone into contact with the water to be treated, which is an optional step, is carried out before the step (A) (in other words, in the arbitrary constituent part as described above). Even when a certain ozone contact tank 10 is provided), in satisfying the condition of (ii) above, the ozone addition amount in the step (A) is added without considering the ozone addition amount in the step (D). It is preferable to determine the amount of hydrogen peroxide added in step (A) based on the amount.

Similar to the ozone contact tank 10, the accelerated oxidation treatment tank 20 introduces ozone generated by an ozone generator 50, which will be described later, into the tank via a second ozone diffuser 52. Then, the accelerated oxidation treatment tank 20 brings the hydrogen peroxide and ozone supplied by the hydrogen peroxide injection device 21 into contact with the water to be treated. At this time, in the accelerated oxidation treatment tank 20, the reaction between ozone and hydrogen peroxide produces a hydroxy radical having a stronger oxidizing power than ozone. By such a hydroxy radical, a substance to be decomposed in the water to be treated, particularly a hardly decomposable substance, can be decomposed well. Furthermore, since ozone is decomposed by the generation of the hydroxy radicals, it is possible to prevent ozone from becoming excessive and reacting with the bromine-containing component and ozone to generate bromate ions. As the accelerated oxidation treatment tank 20 and the hydrogen peroxide injection device 21, general ones can be used.

<Hydrogen peroxide injection device>
The hydrogen peroxide injection device 21 supplies hydrogen peroxide to the accelerated oxidation treatment tank 20 based on the amount of ozone added in step (A). Although FIG. 1 shows a mode in which hydrogen peroxide is directly added to the accelerated oxidation treatment tank 20, hydrogen peroxide may be supplied to the water to be treated on the upstream side of the accelerated oxidation treatment tank 20. The hydrogen peroxide injection device 21 is not particularly limited and can be implemented as a general chemical injection means attachable to a water treatment device. For example, a hydrogen peroxide storage tank, a supply pump, and It can be mounted by a flow control valve or the like.

<Ozone generator>
The ozone generator 50 is in communication with the first ozone diffuser 51 and the second ozone diffuser 52 via the ozone supply pipe 70, and is connected to the ozone contact tank 10 and the accelerated oxidation treatment tank 20 via these. Supply ozone gas. The first ozone diffuser 51 and the second ozone diffuser 52 can be configured by, for example, diffusers having pores, membrane diffusers, or the like. The ozone supply pipe 70 preferably includes a first ozone amount adjusting device 71 and a second ozone amount adjusting device 72. The first and second ozone amount adjusting devices 71 and 72 are not particularly limited as long as the amounts of ozone supplied to the ozone contact tank 10 and the accelerated oxidation treatment tank 20 can be adjusted, and are configured as, for example, flow rate adjusting valves. sell. When the first and second ozone amount adjusting devices 71 and 72 are configured as flow rate adjusting valves, the amount of ozone supplied to each tank 10 and 20 is adjusted by changing the opening degree of the flow rate adjusting valve. be able to. Further, a method of controlling the concentration of the generated ozone gas without changing the flow rate of the ozone gas by using a control signal (electrical signal) to the ozone generator 50 is also applicable. The ozone generator 50 is not particularly limited, and for example, a known ozone generator that converts oxygen into ozone by electrons generated by a discharge phenomenon can be used. As described above, since the ozone contact tank 10 has an arbitrary configuration, when the water treatment device 100 does not include this, the first ozone diffuser device 51 and the first ozone amount adjusting device 71 do not exist. Instead, all the ozone generated by the ozone generator 50 is supplied to the accelerated oxidation treatment tank 20 via the second ozone diffuser 52.

<Reduction treatment tank>
In the reduction treatment tank 30, a reducing agent is added to the water to be treated after the step (A) by the reducing agent injecting device 31, and a hydrogen peroxide remaining in the water to be treated is formed as a water to be treated-reducing agent mixture. The step (B) of decomposing is carried out. As the reducing agent, any reducing agent such as sulfite, thiosulfate, and nitrite can be used as long as it can exhibit a reducing power capable of reducing hydrogen peroxide. Among these, sulfite is preferable because, in addition to the effect of decomposing hydrogen peroxide, reducing the dissolved oxygen concentration in the water to be treated can more effectively suppress foaming in the subsequent step (C).

Then, in the step (B), the pH of the water to be treated-reducing agent mixture is preferably more than 5.0, and more preferably 5.8 or more. The pH of the water to be treated-reducing agent mixture can be usually 8.6 or less. When the pH of the water to be treated-reducing agent mixture exceeds 5.0, the effect of decomposing hydrogen peroxide can be further enhanced. It should be noted that, depending on the properties of the water to be treated and the amount of hydrogen peroxide added, the above conditions are satisfied even if the process for adjusting the pH such as the addition of a pH adjuster is not carried out in the step (B). There are cases. In the reduction treatment tank 30, the pH of the water to be treated-reducing agent mixture is monitored by a pH meter or the like (not shown), and if necessary, a pH adjusting agent injection device 32 or the like is used to adjust the pH adjusting agent such as sulfuric acid and sodium hydroxide. Can be injected.

The redox potential of the water to be treated-reducing agent mixture in step (B) is preferably -200 mV or more and +400 mV or less, and more preferably a value close to 0. When the redox potential of the water to be treated-reducing agent mixture is within the above range, hydrogen peroxide can be well dispersed in the step (B).

<Adsorption treatment tank>
In the adsorption treatment tank 40, a step (C) of passing the water to be treated which has been subjected to the step (B) through the granular material packed bed is carried out. An adsorbent such as powdered activated carbon may be used as the granular material forming the granular material packed layer. Further, the granules constituting the granule-filled layer may contain other granules such as powdered manganese dioxide and powdered iron (III) chloride that can function as a decomposition catalyst. In the step (C), organic substances and the like remaining in the water to be treated after the step (B) can be adsorbed on an adsorbent such as powdered activated carbon. Further, in the case where the granular material constituting the granular material packed layer contains granular material capable of functioning as a decomposition catalyst such as powdered manganese dioxide and powdered iron (III) chloride, it remains in the water to be treated in step (C). It is possible to decompose organic substances and the like. The adsorption treatment tank 40 is not particularly limited, and may have a generally-used configuration such as an activated carbon adsorption tank.

In the water treatment method of the present invention, since the water to be treated in the step (C) has passed through the step (B), the amount of hydrogen peroxide contained in the water to be treated is very small or substantially. It becomes zero, and generation of gas due to decomposition of residual hydrogen peroxide on the surface of the granular material is suppressed. As a result, it is possible to prevent the gas from forming bubbles and blocking the voids (that is, the channels of the water to be treated) in the granular material packed layer. Therefore, the efficiency of the step (C) is less likely to decrease due to the clogging of the granular material packed layer, and the water treatment efficiency can be improved.

Here, the redox potential of the water to be treated after the step (C) is preferably more than 0, preferably +400 mV or less, and more preferably close to 0. If the value of the oxidation-reduction potential of the treated water at the time of passing through the step (C) is a positive value close to 0, it means that the amount of the reducing agent remaining in the treated water after the step (C) is small. .. Therefore, if the redox potential of the water to be treated after the step (C) is more than 0, the residual reducing agent is removed by an oxidizing agent such as hypochlorite and potassium permanganate in the latter stage of the step (C). It is possible to reduce the amount of the oxidizing agent added when carrying out the oxidation step of decomposing, and it is possible to enhance the cost effect. In other words, it is preferable that the oxidation-reduction potential of the water to be treated after the step (C) and before the oxidation step satisfies the above condition. Even if hypochlorite is added to the water to be treated in the former stage of step (A), an oxidizing agent such as hypochlorite is added in the latter stage of step (C). Preferably.

Thus, according to the water treatment method of the present application, after the step (A) of subjecting the water to be treated to accelerated oxidation treatment by a predetermined method, hydrogen peroxide is reacted with a reducing agent to undergo reduction treatment and decomposition ( By carrying out the step (C) of carrying out the adsorption treatment by passing the water to be treated through the granular material packed bed after carrying out B), it is effective that the granular material packed layer is blocked by bubbles due to hydrogen peroxide. It is possible to obtain treated water having a sufficiently low bromate ion concentration while suppressing it.

In addition, the water treatment apparatus 100 capable of suitably implementing the water treatment method of the present application is not particularly limited, and may include any of the following components.

<Control device>
The water treatment device 100 may include the control device 80. The control device 80 preferably further includes an ozone supply amount control device 81 and a hydrogen peroxide supply amount control device 82. The control device 80, the ozone supply amount control device 81, and the hydrogen peroxide supply amount control device 82 are not particularly limited and can be configured by a CPU (Central Processing Unit) or the like. A storage unit (for example, a memory) or the like may be provided.

The ozone supply amount control device 81 can respectively control the amount of ozone supplied to the ozone contact tank 10 and the accelerated oxidation treatment tank 20 based on the measured value of the ozone concentration measured by the dissolved ozone concentration measuring device 61. Further, the hydrogen peroxide supply amount control device 82 can control the amount of hydrogen peroxide supplied to the accelerated oxidation treatment tank 20.

Although the water treatment method of the present invention has been described above with reference to an example, the water treatment method of the present invention is not limited to the above example and can be appropriately modified. For example, in the case of carrying out the step (A) or the step (D), it is of course possible to carry out the step of adding and mixing a coagulant such as polyaluminum chloride (PAC) and performing membrane filtration in the preceding stage. Is.

According to the water treatment method of the present invention, when adopting the accelerated oxidation treatment step in which ozone and hydrogen peroxide are used in combination, it is possible to effectively prevent the granular material packed layer from being clogged with bubbles caused by hydrogen peroxide. Meanwhile, treated water having a sufficiently low bromate ion concentration can be obtained.

10 ozone contact tank 20 accelerated oxidation treatment tank 30 reduction treatment tank 40 adsorption treatment tank 50 ozone generator 51 first ozone diffuser 52 second ozone diffuser 61 dissolved ozone concentration measuring device 62 bromate ion concentration measuring device 70 ozone Supply pipe 71 First ozone amount adjusting device 72 Second ozone amount adjusting device 80 Control device 81 Ozone supply amount control device 82 Hydrogen peroxide supply amount control device 100 Water treatment device

Claims (4)

A water treatment method for obtaining treated water by oxidizing treated water containing a bromine-containing component,
A step (A) of adding ozone and hydrogen peroxide to the water to be treated to accelerate and oxidize the water to be treated;
A step (B) of decomposing hydrogen peroxide remaining in the water to be treated as a water-to-be-treated-reducing agent mixture by adding a reducing agent to the water to be treated after the step (A).
A step (C) of passing the water to be treated which has passed through the step (B) through a granular material packed bed,
at least,
(I) setting the bromate ion concentration in the water to be treated after the step (A) to 15 μg/L or less, or
(Ii) The addition amount of the hydrogen peroxide added in the step (A) is at least twice the addition amount of the ozone on a molar basis.
Including establishing any of
Water treatment method. The water treatment method according to claim 1, wherein the pH of the water to be treated-reducing agent mixture in the step (B) is higher than 5.0. The water treatment method according to claim 1, wherein the reducing agent added in the step (B) is a sulfite. The water treatment method according to any one of claims 1 to 3, wherein the redox potential of the water to be treated after the step (C) is more than 0.

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