WO1999016713A1

WO1999016713A1 - Water quality purification device

Info

Publication number: WO1999016713A1
Application number: PCT/JP1998/004388
Authority: WO
Inventors: Yukio Nakajima
Original assignee: Yukio Nakajima
Priority date: 1997-09-29
Filing date: 1998-09-29
Publication date: 1999-04-08
Also published as: JP3227567B2; JPH11104616A; AU9188398A

Abstract

A water quality purification device for generating extremely fine bubbles and dissolving oxygen components in intake-water from a purification object water zone, and continuously emitting them into the object water zone, comprising an intake pipe (1), an outer shell cylinder (3), an outer shell cylinder (4), a water guide plate (5), a water spray plate (6) equipped with a rotating magnet, a rotary shaft (7) and an underwater motor (8). The vortex flow generated between the rotary inner shell cylinder (4) and the outer shell cylinder (3) mixes air with water to form numerous very fine bubbles and dissolves the oxygen components in the bubbles into intake water. The very fine bubbles coming from above are further divided and converted to finer bubbles by the synergistic operation by the pumping operation and an electromagnetic operation between the water spray plate and the water guide plate (5), and the oxygen components in these bubbles are further dissolved in water.

Description

Description Water purification system Technical field

The invention of this application relates to a water purification treatment method and apparatus for purifying water to be treated, which is polluted and contaminated by organic matter or the like, or is eutrophic and in which algae are propagated.

In particular, polluted by the inflow of industrial wastewater and domestic wastewater, etc. The present invention relates to a water purification treatment method and apparatus for purifying water quality of aquaculture and fishing grounds, and further for purifying water for agricultural use such as hydroponics. Background art

Water purification technology for ponds, moats, canals, lakes, marshes, rivers, shore waters, etc .; The following means have been known as water purification treatment techniques according to (a).

(1) Water purification treatment with mineral water treatment liquid,

(2) Water purification treatment with ozone,

(3) Water purification treatment with activated sludge,

(4) Water purification by biological communication

(5) Water purification treatment by coagulation and sedimentation using industrial chemicals,

(6) Water purification treatment by artificial ultraviolet rays, (7) Water purification treatment by aeration

(8) Water purification treatment by microorganisms (for example, photosynthetic bacteria),

(9) Water purification treatment by the above combination.

A conventional water purification treatment method by aeration will be described.

FIG. 7 is a cross-sectional view of a conventional gas-liquid mixing device.

In Fig. 7, 1 is an intake pipe, 2 is a water intake, 3 is an outer shell, 4 is a rotary inner cylinder, 5 is a water guide plate, s is a sprinkler plate with blades, V is a rotary blade, 7 is a rotary shaft, 8 is a submersible motor and 9 is a column.

The diameter of the rotary inner cylinder 4 is, for example, about 27 mm, and the size of the gap (the first gap gi) between the outer peripheral surface of the rotary inner cylinder 4 and the inner peripheral surface of the outer shell 3 is, for example, For example, it is about 3 to 10 relations. The number of rotations of the rotary inner casing 4 and the rotary sprinkler plate s is, for example, equal to or more than 700 rotations.

When the sprinkler plate s with the blade rotates, the sprinkler plate 5 and the water guide plate 5 cooperate with each other to perform the same function as the centrifugal bomb, so that their peripheral portions become higher than the atmospheric pressure (positive pressure). The lower surface of the inner 简 4 becomes lower than the atmospheric pressure (negative pressure). Therefore, the inside of the first gap g, also has a negative pressure, so that air flows in from the intake pipe 1 and water to be treated flows in from the water absorption pipe 2.

The water to be treated that has flowed into the first gap descends while being rotated at a high speed by the high-speed rotation of the rotary inner cylinder 4. At the same time, a strong swirl occurs.

The inflowing air is efficiently mixed with the water to be treated, forming countless minute bubbles.

The generated bubbles descend together with the water to be treated, flow into the gap (second gap g,) between the water guide plate 5 and the watering plate with blades s, are further divided by the rotating blades V, and are miniaturized. And discharged horizontally to spread to the target water area. Be scattered.

Bubbles diffused into the water to be treated efficiently oxidize various organic substances. The oxidized organic matter aggregates and floats on the water surface. By regularly collecting and removing this, sustainable purification treatment of the water to be treated is achieved.

(This type of gas-liquid mixing device has been used for water purification in various places for many years by the inventor of this application).

A conventional pressurized floating type water purification treatment method will be described.

FIG. 8 is an explanatory view of a conventional one-pressurized microbubble generator.

In Fig. 8, a is a suction port, b is a suction pipe, c is a metering pump, d is a pressure pump, e is a pressurized tank, f is a discharge pipe, and V is a discharge valve.

By the metering pump c, the water to be treated is pumped from the suction to the secondary side of the pump c via the suction pipe b.

8 kg or more of air is injected into the secondary side, and then sent to the pressurized tank e by the pressurized bomb d.

The pressurized air sent into the pressurized tank e is dissolved therein in the water to be treated.

The water to be treated in which the air is dissolved is sent out as it is via the discharge pipe f and discharged from the discharge valve V. In the water area outside the discharge valve V, since the water pressure is about 1 atm, the air dissolved in the water to be treated becomes supersaturated at once, and turns into countless bubbles. At this time, the diameter of the bubble is about 3 micron.

If the water to be treated is too dirty, a flocculant is injected into the suction pipe b by means of a metering bomb (not shown). The injected flocculant and the water to be treated are sufficiently mixed by the pressurizing pump d, and are mixed in the pressurizing tank e. Sent.

A primary coagulation reaction occurs in the pressurized tank e, and a secondary coagulation reaction occurs in the water outside the discharge valve V. Thereby, micro suspended matter is generated. The air bubbles released from the discharge valve V adsorb the generated fine suspended substances, and forcibly levitate them.

After the completion of the water purification by the coagulant, the residual organic matter is oxidized by continuous discharge bubbles from the discharge valve V to maintain the water quality.

In addition, an aerobic bacterium is injected, and the continuous ejection of bubbles promotes their growth, thereby maintaining better water quality.

(The above water purification system using ultra-fine air bubbles is described in “Power Water Purification Examples (1)” published by Power Corporation in July 1997 (1st edition, 2nd printing) No. 94-98 Page)

Finally, a pressurized flotation method using both air bubbles and ions to remove sludge from the bottom of water, such as lakes and marshes that are extremely dirty, will be described.

In this method, fine bubbles of three microphones charged on a brass are attached to an organic substance whose surface is ionized negatively, and the organic substance is floated.

Specifically, the sludge in the target water area is collected in a water tank, and then bubbles are generated by a pressurizing device, and the bubbles are sent to the bottom of the water tank to collect the sludge. Is separated into sludge and water containing organic matter, and sandy mud.

This method removes one-quarter of the organic matter that also increases the chemical oxygen demand (COD). However, removal of ammonia nitrogen from mud after separation must be done by a separate method. (The third on-site experiment since June 1997 by Professor Chiba Institute of Technology on sludge collected from Teganuma, Chiba Prefecture was introduced in a reading newspaper on September 24 of the same year. ).

First, each of the above-mentioned conventional technologies reliably purifies a large amount of water to be treated such as artificial or natural ponds, swamps, rivers, seas, and other fresh water or salt water, or agricultural water or fishery water. However, it was extremely difficult.

Second, it was difficult or impossible to carry out the processing operations continuously. Therefore, it has been difficult or impossible to maintain the water purification action for a long period of time. Third, when a neutralizing agent or a flocculant is used repeatedly, there is a risk that the ecosystem to be treated is damaged.

Fourth, although the acidity and biota of the water to be treated vary widely, it is difficult or impossible for conventional technologies to apply uniformly to such water to be treated. Was.

Fifth, conventional technologies have been too costly to manufacture and operate. Therefore, the burden on local governments, farmers, aquaculture fisheries managers, golf course managers, etc. was too great.

Therefore, the first object of the invention of this application is to reliably purify a large amount of water to be treated, such as artificial or natural ponds, swamps, rivers, seas, or agricultural or aquaculture water. It is an object of the present invention to provide a water purification treatment device that can perform the treatment. A second object of the invention of the present application is to provide a water purification treatment apparatus which can be operated continuously for a long period of time.

A third object of the invention of the present application is to provide a water purification treatment apparatus which has no possibility of damaging an ecosystem.

A fourth object of the invention of the present application is to provide a water purification treatment apparatus that can be applied uniformly even if the acidity and the biota of the water to be treated vary widely. To provide

A fifth object of the invention of the present application is to provide a water purification treatment apparatus which achieves the above first to fourth objects and which is extremely inexpensive in manufacturing cost and operation cost. is there. Disclosure of the invention

In order to solve the above problems and achieve the above object, in the first embodiment, the water purification treatment apparatus according to the present invention includes one or a plurality of intake pipes 1. Including a tube 3, an inner tube 4, a water guide plate 5, a sprinkler plate 6 with a magnet, a rotating shaft 7, a submersible motor 8, and a plurality of struts 9, 9, ...

A bearing 3b is provided at a central point in the top wall of the outer cylinder 3, and a water intake port 2 is provided at one or more points on the upper peripheral wall of the outer cylinder 3, respectively. One or more eccentric points in the top wall of the outer shell 3 or one or more other points on the upper peripheral wall of the outer shell 3 each have an air inlet 3 p. Is drilled,

A relatively large hole is formed in the center of the water guide plate 5,

The sprinkler plate with magnet 6 includes a cultivating plate 6 d and a plurality of permanent magnets 6 m. 6 m,..., And a plurality of filling grooves are radially formed on the upper surface of the rotating plate 6 d. , One of the magnetic poles of each of the permanent magnets 6 m, 6 m... Is embedded in each of the buried grooves, and the other magnetic pole of each of them is projected upward from each of the buried grooves. And

The end portions of the respective intake pipes 1... Are connected to the respective intake holes 3 P,.

The inner periphery of the water guide plate 5 is connected to the lower end of the outer shell 3, and the outer periphery thereof is A plurality of supports 9. 9... Are supported and fixed above the underwater motor 8 by

The upper end of the rotating shaft 7 is rotatably supported by the bearing 3b, and the lower end is connected to the rotating shaft of the submersible motor 8,

The inner cylinder 4 is supported by a rotating shaft 7 on the center axis of the outer cylinder 3, and each intake pipe 1... Is provided between the outer peripheral surface of the inner cylinder 4 and the inner peripheral surface of the outer cylinder 3. The air that has flowed in from each of the water inlets 2... Is mixed with the water to be treated that flows through the water inlets 2. To form a first gap g,

The sprinkler plate with magnet 6 is supported by a rotating shaft 7 in parallel with the water guide plate 5, and a first gap g> between the upper surface of the magnet sprinkler plate 6 and the lower surface of the water guide plate 5> A second gap g for further dividing all the bubbles in the water to be treated which flowed in from the water and further miniaturizing the bubbles, and dissolving oxygen components in each of the bubbles as much as possible in the water to be treated. ₂ are formed.

In the second embodiment,

One or more intake pipes 1,…, outer casing 3, inner casing 4 with magnet, water guide plate 5, sprinkler plate 6 with magnet, rotating shaft 7, underwater motor 8, multiple ,,……

A bearing 3b is provided at a central point in the top wall of the outer cylinder 3, and a water intake port 2 is provided at one or more points on the upper peripheral wall of the outer cylinder 3, respectively. At one or more eccentric points in the top wall of the outer cylinder 3 or at one or more other points on the upper peripheral wall of the outer cylinder 3, the intake holes 3 P,. Is drilled,

On the outer peripheral surface of the magnet-attached inner shell 4, a number of vertically long filling grooves are formed, and in each of the filling grooves, a number of horizontally magnetized permanent magnets 4 m. 4 m. Is embedded in each individual,

A relatively large hole is drilled in the center of the water guide plate 5,

The magnet-equipped watering plate 6 includes a rotating plate 6 d and a plurality of permanent magnets 6 m. 6 m... A plurality of filling grooves are radially formed on the upper surface of the rotating plate 6 d. In each of the buried grooves, one magnetic pole of each of the permanent magnets 6 m. 6 m,... Is buried in each of them, and each of the other magnetic poles is projected upward from each of the buried grooves. ,

The end portions of the intake pipes 1... Are air-tightly and water-tightly connected to the respective intake holes 3 p.

The inner periphery of the water guide plate 5 is connected to the lower end of the outer shell 3, and the outer periphery of the water guide plate 5 is supported above the underwater motor 8 by a plurality of columns 9.9. Fixed,

The inner casing 4 is supported by a rotating shaft 7 on the center axis of the outer casing 3, and each intake pipe 1 is provided between the outer peripheral surface of the inner casing 4 and the inner peripheral surface of the outer casing 3. The air that flows in from the water is mixed with the water to be treated that flows in from each of the water absorption pipes to generate countless fine bubbles, and the oxygen components in each of the air bubbles are mixed into the water to be treated as much as possible. A first gap g, for dissolving the water, is formed, and the sprinkler plate with magnet 6 is supported by a rotating shaft 7 in parallel with the water guide plate 5, and the upper surface of the sprinkler plate with magnet 6 Between the lower surface of the plate 5 and the first gap g, all bubbles in the water to be treated which flowed in from the first gap g, are further divided and miniaturized, and the oxygen component in each of the bubbles is reduced into the water to be treated. for dissolving as much as possible, the second gap g ₂ is formed.

In the third embodiment, In the second embodiment,

A large number of vertically elongated filling grooves are also formed on the inner peripheral surface of the outer casing 3, and a large number of permanent magnets 4 m. 4 m... Magnetized in the horizontal direction are embedded in each of the filling grooves. Have been

Things.

In the fourth embodiment,

In any one of the first to third embodiments,

A plurality of buried grooves are radially formed also on the lower surface of the water guide plate 5, and a plurality of vertically magnetized permanent magnets 5 m. 5 m,. ing,

Things.

In the fifth embodiment,

In any one of the first to fourth embodiments,

Contains ozone or active air generator,

The ozone or active air generator is connected to the upstream of the intake pipe 1 directly or via a blow pipe.

Things. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a longitudinal sectional view of a first embodiment of the water purification treatment apparatus of the present invention.

FIG. 2 is a plan view of a magnet-equipped water spray plate 6 used in the first embodiment of the water purification treatment apparatus of the present invention.

FIG. 3 is a longitudinal sectional view of the outer casing 3 used in the first embodiment of the water purification treatment apparatus of the invention of this application, taken along different cut surfaces. FIG. 4 is an explanatory view of a second embodiment of the water purification treatment apparatus of the present invention.

FIG. 5 is a sectional view of a third embodiment of the water purification treatment apparatus of the present invention.

FIG. 6 is a bottom view of a magnet-provided water guide plate which is a main part of a fourth embodiment of the water purification treatment apparatus of the present invention.

FIG. 7 is an explanatory diagram of a conventional gas-liquid mixing device.

FIG. 8 is an explanatory view of a conventional pressurized floating type water purification / maintenance device. FIG. 9 is an explanatory view of a tiller vortex generated between two rotating cylinders.

FIG. 10 is an explanatory diagram of a method for collecting and detecting ultra-fine bubbles used in an experiment for confirming the effect of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

[First Embodiment]

A first embodiment of the invention of this application will be described.

FIG. 1 to FIG. 3 are explanatory views of a first embodiment of the water purification treatment apparatus of the invention of the present application. Fig. 1 is a cross-sectional view of the device in one longitudinal section, Fig. 2 is a cross-sectional view of only the upper half of the device in another vertical section orthogonal to it, and Fig. 3 is a diagram with a magnet forming a main part of the device. It is a top view of a watering board.

[0 0 1 6]

In Figs. 1 to 3, 1 is an intake pipe, 2.2 is a water intake, 3 is a cylindrical outer shell, and 4 is a cylindrical or cylindrical rotary inner shell. 5 is a water guide plate, 6 is a disk-shaped sprinkler plate with magnet, 6 d is a rotating plate, 6 m is a permanent magnet, 7 is a rotating shaft, 8 is a submersible motor, and 9 is a column. In this embodiment, a long and flexible tube (hose) is used for the intake pipe 1. However, in some cases, an upright and stiff tube is used (see Figure 7). Although the number of the intake pipes 1 is one in FIGS. 1 and 2, it does not prevent the number of intake pipes from being two or more as described later. Outside the water inlet 2, a wire mesh or other dust eliminator can be installed to prevent accidental dust inflow.

A bearing 3b is provided at a center point in the top wall of the outer shell 3.

As shown in the figure, one intake hole 3 p is formed in the upper peripheral wall of the outer cylinder 3. In some cases, the intake hole 3 p can be formed at one eccentric point in the top wall of the outer casing 3. As will be described later, the number of intake holes 3p does not prevent the number of intake holes from being two or more.

In this embodiment, the water guide plate 5 is composed of only an annular plate. The annular plate is formed as a whole in an annular shape by forming a relatively large circular hole in the center of the disk. See Figure 6).

As shown in FIG. 3, the magnet-equipped watering plate 6 includes a rotating plate 6d and three permanent magnets 6m.6m.6m. Each permanent magnet 6 m. 6 m, 6 m is magnetized in the vertical direction. In some cases, the number of permanent magnets can be two, or more than three. If a large number of permanent magnets (six or more) are used, the center part of every other permanent magnet can be cut off to average the magnet spacing.

Each of the permanent magnets used here may be a single permanent magnet, or may be a plurality of small permanent magnets connected in a line. The same applies hereinafter.

Three buried grooves are formed radially (or radially) on the upper surface of the rotating plate 6d. It is. The number of buried trenches can be two, depending on the case, or even more than four.

Three (generally more than one) buried grooves are filled with three (generally more than one) permanent magnets 6 m, 6 m, and 6 m in each lower magnetic pole, but their upper magnetic poles are However, it is projected upward from each filling groove.

Each permanent magnet 6 m. 6 m. 6 m with its upper end protruding upward also serves as a rotating blade in a centrifugal bomb.

(If the permanent magnets 6d of the magnet-equipped watering plate 6 are projected in the horizontal direction, the length of their shadows will expand and contract with the rotation of the watering plate 6. In FIG. The reason that the permanent magnets on the left side of the rotating shaft 7 appear shorter than those on the right side is that their rotational positions happen to be as shown in Fig. 3). Although the number of the struts 9 is four in FIG. 1, it can be two or three in some cases, or can be five or more.

The end (the left end in FIG. 2) of the long and flexible intake pipe 1 is air-tightly and water-tightly connected to an intake hole 3 p formed in the upper peripheral wall of the outer casing 3. The intake pipe 1 is laid below the surface of the water area during operation to prevent the landscape of the target water area from being impaired, and its starting end is to be placed on the ground near the water area. Become.

When the intake port 3p is formed in the top wall of the outer casing 3 as described above, an upright / inflexible pipe body is used as the intake pipe 1, and its end portion (in short, (Lower end) is connected to the intake hole 3P.

The inner periphery of the water guide plate 5 is firmly connected to the lower end of the outer casing 3.

The upper ends of the four (generally plural) columns 9.9, 9, 9 are, for example, welded to the outer periphery of the water guide plate 5 or its vicinity (hereinafter simply referred to as “outer periphery J”. ). The lower ends of the four columns 9.9.9.9.9 are directly connected to the underwater motor 8. These struts can be bent outward or bent. By doing so, the diameter of the magnet-equipped sprinkler plate 6 can be made larger than in FIG.

The underwater motor 8 may be housed in a protective housing or fixed to a mounting table depending on the case. In such a case, the lower ends of the columns 9, 9.9.9 are fixed to a housing or a mounting table. In other words, it is connected to the underwater motor 8 via a housing or a mounting table.

Thus, the water guide plate 5, and thus the outer casing 3, is firmly supported and fixed above the submersible motor 8.

In FIG. 1, the rotating shaft portion (portion near the upper end portion) corresponding to the suction hole 3P is cut away so that the rotation shaft 7 does not obscure the suction hole 3p.

The upper end of the rotating shaft 7 is rotatably supported by a bearing 3 b, and the lower end is connected to the rotating shaft of the submersible motor 8.

The inner cylinder 4 is supported by a rotating shaft 7 on a center axis line in the outer cylinder 3.

A first gap g, is formed between the outer peripheral surface of the inner shell 4 and the inner peripheral surface of the outer shell 3. The first gap mixes the air sucked from the intake pipe 1 with the water to be treated sucked from each of the water inlets 2 and 2 to generate countless minute bubbles, and also converts the oxygen component in each of the bubbles into the air. This is to dissolve as much as possible in the water to be treated.

The sprinkler plate with magnet 6 is supported by a rotating shaft 7 so as to be in parallel with the water guide plate 5.

A second gap g ₂ is provided between the upper surface of the magnet-equipped water spray plate 6 and the lower surface of the water guide plate 5. Is formed. Second gap g _2, for example from 0.7 to 0. Shall be the order of 8 mm. In this gap, all the bubbles in the water to be treated which flowed in from the first gap g, are further divided to be extremely fine, and the oxygen component in each of the bubbles is dissolved as much as possible in the water to be treated. It is to make it.

Next, a method of using the water purification apparatus of the first embodiment and the overall operation will be described.

In the water purification treatment apparatus of this embodiment, the outer casing 3 is completely sunk in advance in the same water area in advance so that the landscape of the target water area is not likely to be damaged.

First gap g, or the second gap g ₂ in the same apparatus, the processed water having entered from the second outer circumferential side of the gap g _2, a and this is filled.

The transmission line for transmitting power from the commercial power source to the underwater motor 8 is laid underground in the target water area so as not to damage the landscape of the target water area.

Next, when the commercial power is turned on and the underwater motor 8 is rotated, power is transmitted by the rotating shaft 7, and the sprinkling plate 6 with magnet and the inner casing 4 are simultaneously rotated.

The number of rotations of the submersible motor 8, that is, the magnet-equipped sprinkling plate 6 and the inner casing 4 is, for example, about 400 rotations or more.

The sprinkler plate with magnet 6 and the water guide plate 5 cooperate to perform the same function as a centrifugal pump.

When the magnet-equipped sprinkling plate 6 rotates, the water to be treated in the _second gap g2 is discharged in the horizontal direction, and the internal water pressure decreases, and becomes equal to or lower than the atmospheric pressure (negative pressure). As a result, the first gap also has a negative pressure, and the water level drops, so that air flows in from the intake pipe 1 and water to be treated flows in from the water absorption pipe 2. The water to be treated that has flowed into the first gap is dragged by the high-speed rotation of the rotary inner cylinder 4 and rotates at a high speed. As a result, the descended water surface in the outer shell 3 violently undulates and bubbling, and countless small eddies as secondary flows are generated below the water surface. The vortex generation mechanism at this time is considered to be almost the same as the tiller vortex generation mechanism shown in Fig. 9. (For details on the Tiller vortex, see “Mechanical Engineering Service (New Edition, Second Printing)”, pages A5-128, published in May 1963, The Japan Society of Mechanical Engineers).

Therefore, the inflowing air is efficiently mixed with the inflowing water to be treated, and becomes innumerable fine bubbles. In addition, the oxygen component in each of the microbubbles is efficiently dissolved into the oxygen-deficient water to be treated.

The water to be treated in the first gap descends while increasing the number of microbubbles and the amount of dissolved oxygen, and the gap between the water guide plate 5 and the rotary sprinkler plate with blades s (second Flows into the gaps g,).

In the second gap g _2, it receives the synergy with Bon Bing effect and electromagnetic action of the blade with the sprinkler plate s, divided with all the microbubbles inflow water being treated and the subdivision and is made, submitted Ultra-fine bubbles of the order of Cron are generated, and the oxygen component in each of the micro-bubbles or the ultra-fine bubbles is further dissolved in the water to be treated.

The water to be treated, which contains microbubbles and dissolved oxygen, is released in the horizontal direction by the bombing action of the rotary sprinkler plate s with blades, and is diffused into the water to be treated.

The microbubbles and dissolved oxygen thus formed do not float up in the water to be treated in a short time and stay in the water for an extremely long time. The present inventors and the practice of the present invention show that they diffuse throughout the water area, and therefore, are significantly superior to the conventional gas-liquid mixing apparatus. It has already been demonstrated by the creators of the form.

The fact that the water purification treatment apparatus according to the present invention is far superior to the conventional gas-liquid mixing apparatus in terms of the degree of fineness of the bubbles and, accordingly, in the length of time during which bubbles and dissolved oxygen stay in water. Was first confirmed experimentally. Therefore, although the reason is still under study, for the moment, the following are considered to be approximately.

As is well known, each water molecule has a hydrogen-oxygen-hydrogen bond state that is not linear, but a polygonal line with an included angle of 105 degrees. The probability distribution is not symmetrical and forms an electric dipole.

Therefore, these water molecules do not exist alone in the liquid phase, and some of them gather together by hydrogen bonding to form a cluster. (The size and shape of the cluster vary depending on the type and amount of dissolved impurities and the temperature.)

However, when water molecules forming an electric dipole are given relative motion with respect to a magnetic field (here, the magnetic field of a permanent magnet), energy (mainly, energy of rotational motion of molecules) (Energy of expansion and contraction movement and translation movement) is given, and the energy level is raised. That is, the water molecules are activated. As a result, it is considered that the cluster of the water molecule becomes smaller, so that oxygen in the bubbles easily dissolves between the clusters, and the bubbles are easily divided.

Further, when the conductive fluid (here, the water to be treated) and the magnetic field make a relative motion, an electric current is induced in the fluid. At the same time, B and ² 2 M isotropic pressure (magnetic pressure) (in here vertical) direction of the magnetic field lines of B ² and tension to occur (supra "Mechanical Engineering flight騖(New Edition Second Printing ) "A5 — See page 61)). These phenomena also make clusters of water molecules smaller, and It is thought that this contributes to facilitating the dissolution of oxygen in the bubbles between the clusters, and to the ease of dividing the bubbles.

On the other hand, oxygen molecules are paramagnetic (that is, they form a magnetic dipole), so when given relative motion with the magnetic field, the energy (primarily the energy of the rotational motion of the molecule and the energy of the translational motion) Energy), and the energy level is raised. As a result, it is considered that oxygen molecules in the magnetic field are activated, and the oxygen molecules on the bubble surface break through the water boundary surface and become easily dissolved therein. (For information on the paramagnetism of oxygen molecules, see, for example, the RIKEN Dictionary published by Iwanami Shoten).

In the first embodiment according to the second gap g ₂ of the invention of this application, the proceeds Bonn Bing action and the and both phenomena at the same time, countless microbubbles flowing is further divided, very fine At the same time, it is considered that the oxygen component in the microbubbles or the microbubbles efficiently dissolves into the water to be treated surrounding the bubbles.

As the diameter of the bubbles released into the water to be treated becomes finer, (1) all the bubbles are prevented from rising to the surface of the water in a short time and acting, and therefore the water resistance time is limited. (2) The surface area of the entire bubble, that is, the contact area between the whole bubble and the water to be treated becomes infinitely large.

Thus, the dissolved oxygen and ultrafine bubbles diffused into the water to be treated efficiently oxidize various organic substances. The micro-suspended matter (S S) generated by the oxidation adheres to the subsequent air bubbles, floats on the water surface, and aggregates to form floating scum.

In addition, when sunlight is present, planktonic algae (eg, aoko) can be killed and aggregated. Destruction of floating algae · Micro-suspended matter generated by aggregation is attached to air bubbles and floats on the surface of the water, resulting in floating scum. Become.

In addition, these microbubbles can be innumerably bound to the bottom of the water (microbial layer) to give them buoyancy and float in large units. (During the experiment, a lump with a diameter of about 20 to 30 centimeters surfaced, and sometimes a monstrous sound was heard.)

The above facts have also been observed by the inventor and the creator of the embodiment of the present invention.

The floating scum is periodically collected by appropriate means and disposed of, and is disposed of, so that the water purification process for the target water area can be achieved with sustainability. It is.

[Second embodiment]

A second embodiment of the invention of this application will be described.

FIG. 4 is a sectional view of the second embodiment.

In FIG. 4, 1 is an intake pipe, 2 and 2 are water intake ports, 3 is a cylindrical outer cylinder, 4 is a cylindrical or cylindrical inner cylinder with a magnet, and 4 m. In this embodiment, permanent magnets are newly introduced, 5 is a water guide plate, 6 is a disk-shaped sprinkler plate with magnet, 3 m is a permanent magnet, 7 is a rotating shaft, 8 is a submersible motor, and 9 is a column. .

The above-mentioned members are the same as those of the first embodiment except for the inner shell 4 with a magnet.

In the second embodiment, a large number of vertically long filling grooves are formed on the outer peripheral surface of the inner casing 4. A large number of permanent magnets 4 m. 4 m,..., Which are magnetized in the horizontal direction, are embedded in each of the filling grooves.

The permanent magnets 4 m. 4 m... May be arranged discretely in the vertical direction (vertical direction) of the inner casing 4 as shown in the figure, and may be arranged throughout the vertical direction. They may be arranged so as to be continuous.

The outer peripheral surface of the magnet-equipped inner cylinder 4 is flush in FIG. 4, but the permanent magnets 4 m. 4 m... May be slightly projected.

As in the first embodiment, a first gap g is formed between the outer peripheral surface of the magnet-attached barrel 4 and the inner peripheral surface of the outer casing 3.

In the first gap, a negative pressure (atmospheric pressure or lower) results in a negative pressure (atmospheric pressure or lower), and the water level drops.

The water to be treated that has flowed into the first gap is rotated at a high speed by the high-speed rotation of the inner casing 4 with magnets, similarly to the first embodiment. As a result, the descending water surface in the outer shell 3 undulates violently, and countless vortices are generated as secondary flows below the water surface.

Therefore, the inflowing air is efficiently mixed with the inflowing water to be treated, and becomes innumerable fine bubbles. The oxygen component in each of the microbubbles is efficiently dissolved in the water to be treated. This is the same as in the first embodiment.

However, in the second embodiment, a large number of permanent magnets 4 m. 4 m,... Are embedded in the outer peripheral surface of the inner casing 4, so that each point in the first gap g is horizontal. Since the magnetic field in the direction (strictly speaking, the radial direction) is generated, the interaction between the magnetic field and the water molecule, the induced current and the water molecule are the same as in the second gap g, in the first embodiment. Interaction with the magnetic field and the oxygen molecules, and their synergistic effects, generate finer bubbles in the water to be treated in the first gap g ». More oxygen components in the bubbles can be dissolved in the water to be treated.

Other items of the second embodiment are the same as those of the first embodiment. is there.

[Third Embodiment]

A third embodiment of the invention of this application will be described.

FIG. 5 is a sectional view of the third embodiment.

In FIG. 5, 1 is an intake pipe, 2.2 is a water intake, 3 is a cylindrical outer shell with a magnet, 3 m. 3 m. '"Is a permanent magnet newly introduced in this embodiment, 4 is a cylindrical inner cylinder with magnets, 4 m. 4 m... Are permanent magnets, 5 is a water guide plate, 6 is a disk-shaped sprinkler plate with magnets, 6 d is a rotating plate, 6 m is a permanent magnet, 7 Is a rotating shaft, 8 is a submersible motor, and 9 is a column.

The above members are the same as those of the second embodiment except for the outer shell with magnet 3.

In the third embodiment, in addition to the outer peripheral surface of the inner cylinder 4, a large number of vertically long filling grooves are formed on the inner peripheral surface of the outer cylinder 3.

A large number of permanent magnets 3 m, 3 m..., Which are magnetized in the horizontal direction, are embedded in each of the filling grooves.

In the third embodiment, the magnetic field in the first gap is strengthened by the action of the large number of permanent magnets 3 m. 3 m... The interaction between the action, the induced current and the water molecules, and the interaction between the magnetic field and the oxygen molecules are also strengthened, and the synergistic effect of them produces finer bubbles in the water to be treated in the first gap. Further, more oxygen components in the bubbles can be dissolved in the water to be treated.

The rest of the third embodiment is the same as the second embodiment.

[Fourth embodiment] A fourth embodiment of the invention of this application will be described.

FIG. 6 is a bottom view of a water guide plate with magnets, which is a main part of the fourth embodiment.

In FIG. 6, 5 is a water guide plate with a magnet, 5 d is an annular plate, 5 m. 5 m... Are permanent magnets. Other members are the same as those in the first to third embodiments.

In this embodiment, the water guide plate with magnet 5 is composed of an annular plate 5d and three (generally a plurality of) permanent magnets 5m, 5m and 5m. The annular plate 5d has an annular shape as a whole due to the presence of a relatively large circular hole 5c in the center. In the fourth embodiment, a plurality of filling grooves are radially formed also on the lower surface (bottom surface) of the annular plate 5d.

In each of the buried grooves, three (generally plural) permanent magnets 5 m, 5 m, 5 m, which are magnetized in the vertical direction, are embedded.

[0 0 3 3]

In the fourth embodiment, in addition to the outer peripheral surface of the inner cylinder 4 and the inner peripheral surface of the outer cylinder 3, the permanent magnets 5 m, 5 m, and 5 m are embedded in the lower surface of the water guide plate 5. Therefore, finer bubbles can be generated in the water to be treated, and more oxygen components in the bubbles can be dissolved in the water to be treated.

And thus, in the fourth embodiment, the permanent magnets 5 m of three in the water guide plate 5 with the magnets (plurality in General), 5 m. By the action of 5 m, during the second gap g ₂ The interaction between the magnetic field and the water molecules, the interaction between the induced current and the water molecules, and the interaction between the magnetic field and the oxygen molecules are also strengthened due to the strengthened magnetic field inside. Air bubbles are generated in the water to be treated in the _second gap g2, and the oxygen component in the air bubbles is larger. It is dissolved in the water to be treated.

The other matters of the fourth embodiment are the same as those of the first to third embodiments.

[0 0 3 4]

[Fifth Embodiment]

A fifth embodiment of the invention of this application will be described.

In the fifth embodiment, an ozone generator or an active air generator is used together.

In this embodiment, the ozone generator or the active air generator is installed on the ground, and an intake hole 3 p formed in the upper peripheral wall of the outer shell 3 through a long and flexible intake pipe 1. The connection is airtight and watertight. The intake pipe 1 will be laid below the surface of the water area during operation so that the landscape of the water area to be treated is not damaged. The ozone or active air generated by those devices is sent into the inside of the outer casing 3 through the flexible intake pipe 1 and the intake port 3p.

However, in the case where the air intake hole 3P is formed at an eccentric point in the top wall of the outer cylinder 3, the ozone generator or the active air generator may be provided above the outer cylinder 3 and above the water surface by appropriate means. Fixed at. The ozone or active air generated by these devices is similarly sent into the inside of the outer casing 3 through the upright and rigid intake pipe 1. At this time, the main body of the water purification treatment device must be firmly held so as not to fall.

In the fifth embodiment, instead of mere air, air containing ozone or active air is sent to the intake pipe 1, so that the water purification action is further enhanced by the synergistic action of these and air bubbles. Can be promoted. Other items of the fifth embodiment are similar to those of the first to fourth embodiments. It is.

[0 0 3 5]

[Sixth Embodiment〗

A sixth embodiment of the invention of this application will be described.

If rainwater or the like flows into the water area to be treated and the water surface fluctuates, the water depth and water pressure of the intake air 2 fluctuate, and the optimal mixing ratio of the water to be treated and air is disrupted. Then, the generated bubbles become larger than expected, which hinders water purification.

In this embodiment, in order to cope with fluctuations in the water surface of the water area to be treated, the main body of the water purification treatment device is connected to an appropriate float and floated from the bottom of the water. Therefore, the water depth and the water pressure of the intake manifold 2 are also kept from fluctuating.

Other items in the sixth embodiment are the same as those in the first to fifth embodiments.

[0 0 3 6]

[Seventh Embodiment]

A water purification treatment method according to a seventh embodiment will be described.

When the water to be treated is very dirty or acidified, it is only for the first time period for immediate improvement. Watering or spraying. As a result, the organic substances are forcibly levitated, and the pH is improved.

After the improvement by the chemical, the water purification is continued by the methods and apparatuses according to the first to sixth embodiments.

At a stage where water purification has progressed to some extent, bacteria (aerobic bacterium to ammonia decomposition bacteria) will be introduced. Due to the above synergistic effects, the water to be treated can be sufficiently purified at the end.

[0 0 3 7]

[Method of collecting and detecting fine bubbles]

A method for collecting and detecting microbubbles will be described.

Bubbles that immediately rise to the surface of the water near the water purification treatment device operating in the target water area are easily visible, but such bubbles have a large diameter and thus contribute little to water purification.

Bubbles that can contribute to water purification are considered to be 2-3 micron diameters or smaller. Therefore, the existence of such bubbles cannot be confirmed by hand. Observation with a microscope is probably not effective, since the bubbles are lost during the pretreatment stage. Furthermore, it is theoretically impossible to discriminate, by light, the presence or absence of a bubble whose wavelength is below the wavelength of light (submicron order).

Hereinafter, a method for collecting and detecting fine bubbles used in an experiment for confirming the effect of the present invention will be described with reference to FIG.

(0) Prepare a wide-mouthed transparent container w.

(1) Submerge the transparent container w below the surface of the target water area, with the container facing upward as shown in Fig. 10 (a). The transparent container w is filled with the water to be treated.

(2) Turn the transparent container w under the water.

[0 0 3 8]

(3-1) Pull up the outer surface of the bottom wall of the transparent container w that has been inverted below the water surface to the water surface as shown in Fig. 2. (3-2) Alternatively, as shown in Fig. 3, the water is pulled up to the vicinity of the wide mouth on the water surface. Then, since the water pressure in the transparent container w decreases, the dissolved gas is easily bubbled. In either case, the inverted inner surface of the bottom wall acts as a trap for bubbles that float.

(4) Hold this state of the transparent container w for a while.

(5) The microbubbles inside or below the transparent container w float as they are or mutually. Alternatively, the dissolved gas bubbles and floats. The air bubbles that have floated are collected on the inner surface (trap) of the bottom wall. The trapped bubbles combine with each other to form larger bubbles.

(6) Observe the enlarged bubbles with the naked eye (final).

When the water pressure in the transparent container w is to be reduced in step (3-2), the height of the container w should be as large as possible.

According to the above-mentioned collection and detection method, it was found that a small amount of air bubbles could be collected in the transparent container w even after 30 minutes or more and about one hour had elapsed after the operation of this device was stopped. It is thought that the diameter of the microbubbles before collection, which had stayed in the water for 30 minutes to 1 hour, would be about 2 to 3 micron or less.

[0 0 3 9]

[Effect confirmation experiment 1 1

In order to create a water area to be treated for experiments, a 2.5-meter-diameter, 1.2-meter-high aquaculture fishery was installed in the courtyard of the factory where the water purification treatment device of the present invention was prototyped. 'A resin tank was installed, about 5 tons of fresh water was charged, and a trial run of the device was performed.

The fact that the ultra-fine bubbles generated and released by the device reached the periphery of the tank was confirmed by applying the method shown in Fig. 10 (b) and trapping the bubbles in a transparent container. This was confirmed (June 13, 97). Based on the results mentioned above, organic fertilizer (3 bags of fermented chicken dung containing 20 kilograms manufactured by Biocera Mix Co., Ltd.) was put into the tank for 12 days. Allowed to ferment. As a result, the water became excessively dirty and opaque, and even the threads grew to a great extent, and the entire courtyard of the factory emitted a strong odor. (June 14 to June 25, 1997).

[0 0 4 0]

At the above stage, the water purification treatment device shown in Figs. 1 to 3 was sunk into the center of the water tank, and a continuous 30-hour test operation was started. It was confirmed that the bubbles caused the dirt to float without interruption. (June 25, 1997, 10: 30-26, 17:02) On the second day, under the sunshine, the bubbles with dirt However, it was confirmed that the surface of the aquarium became full in about an hour and a half, and the work to rescue the bubbles with a net was continued throughout the day (at 10:30 on June 26, 2010). 17 o'clock).

(During this time, the feel of the experimenter (the creator of this device) has obtained that it will take more than ten times the working time (300 hours) to achieve complete purification. It was a thing).

For about 12 hours from 10:30 am on the second day, the water purification equipment was operated again while brushing a total of 5 tons of water (from 26:30 to 22:30 to 10:00 on February 27). Half)

At 10:30 am on the third day, after the operation was stopped, the organic fertilizer was added again. Water supply was intermittent until 14:30 on the same day. At around 14 o'clock on the same day, the amount of foam on the surface of the tank also began to decrease. The weather on the day was occasionally rainy (10: 30-17: 00 on the 27th).

[0 0 4 1]

On the fourth day, the odor was almost gone. A test run was carried out for about one hour from 15:00. Bubbles containing dirt appeared on the surface of the aquarium, forming complex wrinkles in the shape of a spiral nebula, and then flowing around the aquarium. However, high bubbles like the second day do not occur I got it. It was judged that the weather on that day was cloudy and sometimes rainy, and that photosynthesis was not performed, and thus algae (mainly aoko) could not grow.

The fact that the ultrafine bubbles generated and released by the water purification treatment equipment are floating in the water is due to the fact that a transparent container is placed in the water area around the periphery of the water tank and the collection and detection method shown in Fig. 10 (b) is used. With this, it was easy to confirm. The agent was present at the experiment on the day (15--16, March 28). Also, according to the report of the experimenter, it was found that the method of FIG. 10 (c) succeeded in collecting dissolved bubbles even two days after the operation was stopped.

[0 0 4 2]

[Effect confirmation experiment 2]

97 On August 8, 2007, `` Kanuma, Tochigi Prefecture, Japan '' 72 2 Golf Country Hall 7 The water purification system shown in Figures 1 to 3 was installed under the water near the center of the artificial pond beside Hole 7. Then, continuous operation for a long period was started.

The water area of this artificial pond is estimated to be 80 meters long, 70 meters wide and slightly more than 1 meter deep in the center, and an estimated 5,000 tons of water to be treated is estimated. Is filled with. As for the water in this pond, the rainwater that once infiltrated the lawn springed out of the water vein around the pond again and flowed as a rivulet, and liquid fertilizer and pesticides sprayed on the lawn flowed in at any time. Is considered to be unique.

Anyway, about one week after the installation of this device, white wrinkle-like suspended matter first started to emerge. The floating material at this time was a reaction product formed by oxidation from the microbubbles or dissolved oxygen from the apparatus.

[0 0 4 3]

On a sunny day, aoko is actively consumed by consuming nitrogen and phosphorus. It proliferates, and the proliferated ako dies and reacts with microbubbles or dissolved oxygen. They were collected and combined with the subsequent air bubbles to give buoyancy and to float on the water surface.

It was observed that these suspended matter was blown downwind when there was a wind, and slowly swept to the shore in the form of a spiral nebula when there was no wind. In addition, it was observed that floating suspended solids that had been agglomerated were also likely to be dispersed again in the target water when exposed to rain.

Furthermore, as observed at noon on September 13 (35 days after the start of operation), despite the slight rainfall on the previous day and on that day, the dead cocos continued along the shore, and It was floating. The agent was present to observe on this day. According to the above experimental results, it floated by reacting with the ultra-fine bubbles or dissolved oxygen generated and released by this device, and then it was blown to the shore by wind, or concentric flows Most of the nitrogen and phosphorus in the water area to be treated is finally removed by continuously or intermittently removing the floating and floating substances flowing on the sea by known means such as oil fence. It was also found that oxygen deficiency, nitrite (biotoxin) generation, turbidity, etc. could be eliminated. Industrial applicability

Since the invention of this application is configured as described above, the following remarkable effects can be obtained.

(a) It is possible to generate finer bubbles than a conventional gas-liquid mixing device. Therefore, air bubbles can be retained for a long time. Therefore, it is possible to reach farther by using the water flow.

(b) Therefore, it is possible to surely purify the water quality even for a huge amount of water to be treated. It can also be applied to non-closed water areas with flowing water.

(c) The processing equipment can be operated continuously. Therefore, water purification The effect can be maintained for a long time.

(d) There is no risk of damaging the ecosystem.

(e) Even if the acidity and biota of the water to be treated vary widely, they can be applied uniformly.

(f) The cost of water purification can be significantly reduced. Therefore, the burden on local governments and various management entities can be greatly reduced.

Claims

The scope of the claims

1.1 or a plurality of intake pipes (1.), Outer shell (3), inner shell (4), water guide plate (5), watering plate with magnet (6), rotating shaft (7 ), A submersible motor (8), and a plurality of struts (9.9.).

A bearing (3b) is disposed at a center point in the top wall of the outer cylinder (3), and one or more points on the upper peripheral wall of the outer cylinder (3) are respectively provided with a water inlet (2). ~) Are drilled and one or more eccentric points in the top wall of the outer shell (3) or one or more other eccentric points in the upper peripheral wall of the outer shell (3) Each of the points has a hole (3 p,…)

A relatively large hole is formed in the center of the water guide plate (5). The magnet-equipped water spray plate (6) includes a rotating plate (6d) and a plurality of permanent magnets (6 m. ..), And a plurality of buried grooves are radially formed on the upper surface of the rotating plate (6 d), and each of the permanent magnets (6 m. m...) are embedded in each individual, and the other magnetic poles of each are protruded upward from each of the embedded grooves to each individual,

The end portions of the intake pipes (1...) Are air-tightly and water-tightly connected to the intake holes (3p,...) Of the outer shell (3), respectively.

An inner peripheral portion of the water guide plate (5) is connected to a lower end portion of the outer casing (3), and an outer peripheral portion thereof is connected to the underwater motor by the plurality of columns (9.9). (8) Above, supported and fixed,

The upper end of the rotating shaft (7) is rotatably supported by the bearing (3b), and the lower end is connected to the rotating shaft of the submersible motor (8).

The inner shell (4) is located on the center axis of the outer shell (3), (7)

Between the outer peripheral surface of the inner shell (4) and the inner peripheral surface of the outer shell (3), the air flowing in from each of the intake pipes (1, 1) is introduced into the respective water inlets (2.). The first gap (g :) for mixing with the water to be treated flowing from the water to generate countless minute bubbles and dissolving the oxygen component in each of the bubbles as much as possible in the water to be treated is formed. Formed,

The sprinkler plate with magnet (6) is supported by the rotating shaft (7) in parallel with the water guide plate (5),

Between the upper surface of the magnet-equipped water spray plate (6) and the lower surface of the water guide plate (5), all the bubbles in the water to be treated which flowed in from the first gap (g,) are further divided. A second gap (g ₂ ) is formed for minimizing the size of the air bubbles and dissolving the oxygen component in each of the bubbles as much as possible in the water to be treated.

Water purification treatment equipment.

2.1 or more intake pipes (1.), Outer casing (3), inner casing with magnet (4), water guide plate (5), sprinkler board with magnet (6), rotating shaft (7), a submersible motor (8), and a plurality of columns (9.9), and a bearing (3b) is arranged at a center point in the top wall of the outer casing (3). At one or more points on the upper peripheral wall of the outer shell (3), a water inlet (2.) is drilled, and one or more water inlets (2.) in the top wall of the outer shell (3) are provided. Each of the eccentric points or one or more other points on the upper peripheral wall of the outer casing (3) is provided with an intake hole (3p...)

On the outer peripheral surface of the inner cylinder with magnet (4), a number of vertically elongated filling grooves are formed, and in each of the filling grooves, a number of permanent magnets (4m, 4m) magnetized in the horizontal direction are provided. ..) is embedded in each item, A relatively large hole is formed in the center of the water guide plate (5). The magnet-equipped water spray plate (6) includes a rotating plate (6d) and a plurality of permanent magnets (6 m). . 6 m), and a plurality of buried grooves are radially formed on the upper surface of the rotating plate (6 d), and each of the buried grooves is provided with each of the permanent magnets (6 m, 6 d). m. are embedded in each of the individual poles, and the other poles of each of them are respectively protruded upward from each of the burial grooves,

The end portions of the intake pipes (1,...) Are air-tightly and water-tightly connected to the intake holes (3 p,...) Of the outer casing (3).

The inner periphery of the water guide plate (5) is connected to the lower end of the outer casing (3), and the outer periphery of the water guide plate (5) is connected to the plurality of columns (9, 9,...). Therefore, it is supported and fixed above the underwater motor (8),

The inner shell (4) is supported by the rotating shaft (7) on the center axis of the outer shell (3),

Between the outer peripheral surface of the inner shell (4) and the inner peripheral surface of the outer shell (3), the air flowing in from each of the intake pipes (1. ·) The first gap (g) for mixing with the water to be treated flowing from above to form countless fine bubbles and dissolving the oxygen component in each of the bubbles as much as possible in the water to be treated. ,) Are formed,

Between the upper surface of the magnet-equipped watering plate (6) and the lower surface of the water-guiding plate (5), all air bubbles in the water to be treated flowing from the first gap (g,) are provided. And a second gap (g ₂ ) for dissolving the oxygen component in each of the bubbles in the water to be treated as much as possible is formed.

Water purification treatment equipment.

3. A large number of vertically long filling grooves are also formed on the inner peripheral surface of the outer casing (3),

A number of permanent magnets (4 m. 4 m...) Magnetized in the horizontal direction are embedded in each of the filling grooves.

3. The water purification treatment device according to claim 2.

4. A plurality of buried grooves are also radially formed on the lower surface of the water guide plate (5), and each of the buried grooves has a plurality of vertically magnetized permanent magnets (5 m .5 m. ·) Is embedded in each,

The water purification treatment device according to any one of claims 1 to 3.

5. Contains ozone or active air generator,

The ozone or active air generator is connected directly before or through the air pipe to the upstream of the intake pipe (1...).

The water purification treatment apparatus according to any one of claims 1 to 4,