JP2007083179A - Treatment method and apparatus for copper particle-containing water - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enable a recovery of copper and preparation of treated water with a releasable excellent water quality by efficiently precipitating copper particles in copper particle-containing water and subjecting the water to solid-liquid separation. <P>SOLUTION: In a copper particle-containing water treatment method, copper ions are added to and mixed with the copper particle-containing water; pH is adjusted to 8-10 to generate flocs of copper hydroxide; the copper particles are incorporated into the flocs, and then solid-liquid separation is carried out. It is desirable that the solid-liquid separation is carried out by using a filter device having a floating filter medium layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method and apparatus for treating copper-containing water that efficiently removes copper particles in copper-containing water.

  Since copper is a valuable metal, it is recovered and used as a copper raw material by removing copper from wastewater containing a large amount of copper. For example, as a method for treating wastewater containing copper as copper ions, there is a method in which alkali is added to the wastewater to insolubilize the copper as copper hydroxide and solid-liquid separation is performed. In Japanese Patent No. 3593726, sulfuric acid coexists. There has been proposed a method of solid-liquid separation of copper insolubilized material by adding alkali to copper-containing wastewater.

  On the other hand, if it is the waste water which contains copper not as a copper ion but as a solid copper particle, it is thought that a copper particle can be collect | recovered by carrying out a solid-liquid separation process.

  However, the copper particle-containing water discharged from the copper product polishing process or the like has a variety of particles from fine copper particles having a particle size of about 0.1 to 10 μm to relatively coarse copper particles having a particle size of about 10 to 100 μm. It contains a large amount of copper particles having a diameter, and as it is, the copper particles hardly settle even if left for a long time.

The difficulty of sedimentation of the copper particles in the copper particle-containing water hardly changes even when a polymer flocculant is added to the copper particle-containing water before the solid-liquid separation. In addition, even if a certain amount of copper particles are separated and removed by sedimentation for a long time, since the separated water still contains fine copper particles, it cannot be discharged as it is.
Japanese Patent No. 3593726

  The present invention has been made in view of the above-described conventional circumstances, and efficiently collects copper particles in copper particle-containing water and separates them into solid and liquid to recover copper, and has good water quality that can be discharged. It aims at providing the processing method and apparatus of copper particle containing water which can obtain the treated water of this.

  The copper particle-containing water treatment method of the present invention (Claim 1) adds copper ions to copper particle-containing water, adjusts the pH to 8 to 10 to generate a copper hydroxide floc, and the floc It is characterized in that copper particles are taken in and then solid-liquid separation is performed.

  According to a second aspect of the present invention, there is provided a copper particle-containing water treatment method according to the first aspect, wherein the solid-liquid separation is performed using a filtration device having a floating filter medium layer.

  The copper particle-containing water treatment method according to claim 3 is the floating filtration device according to claim 2, wherein the filtration device has a filtration layer made of a floating filter medium formed in a cylindrical filtration tower with the cylinder axis direction being the vertical direction. The raw water is introduced into the lower part of the filtration layer in the swirling direction to generate a swirling flow in the lower part of the filtration layer, and a part of the floating filter medium is taken out from the lower part of the filtration layer and again the filtration layer A filter medium circulating means to be introduced into the lower part, a sediment receiving tank for separating the floated filter medium from the floated filter medium-containing sediment by introducing the floated filter medium-containing sediment from the bottom of the filtration tower, and the sediment receiving tank. A floating filter medium returning means for guiding the floating filter medium from which the solid content has been separated to the raw water introduction pipe, and the floating filter medium returning means has an ejector-type suction means provided in the raw water introduction pipe, The sediment is received by the ejector type suction means. It was aspirated floating filter media from and characterized in that for returning the raw water inlet pipe.

  The copper particle-containing water treatment apparatus of the present invention (Claim 4) adjusts the pH of the mixing water obtained by adding copper ions to the copper particle-containing water and the mixed water obtained by the mixing means to 8 to 10. A pH adjusting means for generating a copper hydroxide floc and taking copper particles into the floc; and a means for solid-liquid separation of water from the pH adjusting means.

  The copper particle-containing water treatment apparatus according to claim 5 is characterized in that, in claim 4, the solid-liquid separation means is a filtration apparatus having a floating filter medium layer.

  The copper particle-containing water treatment apparatus according to claim 6 is the floating filtration apparatus according to claim 5, wherein the filtration apparatus has a filtration layer formed of a floating filter medium in a cylindrical filtration tower having a cylinder axis direction as a vertical direction. The raw water is introduced into the lower part of the filtration layer in the swirling direction to generate a swirling flow in the lower part of the filtration layer, and a part of the floating filter medium is taken out from the lower part of the filtration layer and again the filtration layer A filter medium circulating means to be introduced into the lower part, a sediment receiving tank for separating the floated filter medium from the floated filter medium-containing sediment by introducing the floated filter medium-containing sediment from the bottom of the filtration tower, and in the sediment receiving tank A floating filter medium returning means for guiding the floating filter medium from which the solid content has been separated to the raw water introduction pipe, and the floating filter medium returning means has an ejector-type suction means provided in the raw water introduction pipe, The sediment is received by the ejector type suction means. It was aspirated floating filter media from and characterized in that for returning the raw water inlet pipe.

According to the present invention, copper particles in water containing copper particles are smoothly incorporated with a good coprecipitation effect by incorporating them into a floc of copper hydroxide (Cu (OH) ₂ ) produced by insolubilizing copper ions. Can be allowed to settle. For this reason, even if it is copper particle containing water with poor sedimentation property of copper particles, copper is recovered by an efficient solid-liquid separation process, and after being subjected to a slight post-treatment as it is or as necessary Therefore, it is possible to obtain treated water with good water quality that can be discharged.

  It should be noted that iron particles (for example, ferric chloride), or iron ions and clay minerals such as kaolin, are added instead of copper ions to adjust the pH to alkaline, so that the copper particles are incorporated into the iron hydroxide floc and solidified. Although liquid separation is possible, in this case, the recovered sludge contains copper and iron, or further kaolin, which is disadvantageous for the recovery and reuse of copper.

  According to the present invention, the copper particles can be taken into the flocs of copper hydroxide and efficiently settled. However, the sedimentation property is not sufficient, and there are flocs that easily float. Therefore, in the present invention, it is preferable that solid-liquid separation is performed using a filtration device having a floating filter medium layer, and flocs that are likely to settle are settled and separated, and flocs that are likely to float are captured by the floating filter medium layer. Item 2, 5).

  And, as a filtration device having this floating filter material layer, in a floating filtration device in which a filtration layer made of a floating filter material is formed in a cylindrical filtration tower whose vertical direction is the cylinder axis direction, raw water is supplied to the lower part of the filtration layer. Raw water introduction pipe for introducing a swirl flow in the lower part of the filtration layer by introducing in the swirl direction, a filter medium circulating means for taking out a part of the floating filter medium from the lower part of the filter layer and introducing it again into the lower part of the filter layer, and the filtration tower The raw water is introduced into the sediment receiving tank for separating the floated filter medium from the floated filter medium-containing sediment from which the floated filter medium-containing sediment is introduced, and the solid material separated in the sediment receiving tank. A floating filter medium returning means for guiding to the pipe, the floating filter medium returning means having an ejector type suction means provided in the raw water introduction pipe, and the floating filter medium from the sediment receiving tank by the ejector type suction means. Suck Preferably the raw water introduced is to return to the pipe floating filtration device (claim 3, 6), if the floating filtration device, can perform efficient solid-liquid separation based on the following effects.

(1) Since the lower part of the filtration layer by the floating filter medium swirls and flows, the lower surface part of the filtration layer is not easily clogged with suspended substances. Therefore, the filtration operation can be continued with a low pressure loss even if the frequency of washing is reduced. Further, even when a floating filter medium having a small particle size is used, an increase in pressure loss due to clogging is sufficiently suppressed.
(2) During filtration operation, a part of the floating filter medium is taken out from the lower part of the filter layer and introduced again into the lower part of the filter layer. The filter medium re-introduced into the lower part of the filter layer collides with the filter layer. Thus, the lower part of the filtration layer is disturbed, and the formation of the swirling fluidized bed and the update of the lower part of the filtration layer are promoted. Moreover, since the deposit | attachment adhering to a filter medium peels by the collision of a filter medium, the clogging of a filtration layer is suppressed.
(3) When the filtration operation is performed, solid matter adheres to the floating filter medium, and a part of the floating filter medium settles at the bottom of the filtration tower. The floated filter medium-containing sediment is introduced from the filtration tower into the sediment receiving tank, and the floated filter medium and the attached solid matter are separated in the sediment receiving tank. The floating filter medium floats in the sediment receiving tank and is returned to the filtration tower through the raw water introduction pipe.
(4) Ejector type suction means is provided in the raw water introduction pipe, and the floating filter medium in the sediment receiving tank is sucked and guided to the raw water introduction pipe by this ejector type suction means. Smoothly transferred to the raw water introduction pipe. For this reason, the floating filter medium is prevented from remaining in the sediment receiving tank.

  The levitation filter medium of this levitation filter device includes a large particle size filter medium having a relatively high specific gravity and a large particle size, and a small particle size filter medium having a relatively low specific gravity and a small particle size. The upper side of the filtration layer is constituted, and the lower side of the filtration layer is constituted by the large particle size filter medium, and raw water is introduced into the middle part of the filtration layer made of the large particle size filter medium during the filtration operation. At the time of operation, it is preferable that a fixed layer made of a small particle size filter material, a fixed layer made of a large particle size filter material, and a fluidized bed made of a large particle size filter material are formed in order from the top in the filtration layer. According to the floating filtration device, since the lower part of the filtration layer is a fluidized bed made of a large particle size filter medium, clogging of the filtration layer can be suppressed over a long period of time. Moreover, since the upper part of a filtration layer consists of a small particle size filter medium, highly purified filtration water can be obtained.

  Further, in this case, it is preferable that a filter having a smaller opening than the large particle size filter medium is provided in the sediment receiving tank, and the filter passing material is preferably discharged from the sediment receiving tank. Thus, the filter provided in the sediment receiving tank prevents the filter medium from flowing out. Since the opening of the filter is relatively large, clogging of the filter is also suppressed.

  Furthermore, in this case, it is preferable that an upper chamber and a lower chamber partitioned by a filter are provided in the sediment receiving tank, and a means for supplying gas to the lower side of the filter is provided. Thus, by introducing a gas such as air to the lower side of the filter, the floating filter medium to which the solid content has adhered is stirred in the sediment receiving tank, and the adhered solid content is efficiently separated from the floating filter medium. The Moreover, the sludge solidified in the sediment receiving tank is loosened and becomes fine and can be discharged through the filter.

  Furthermore, in this case, it is preferable to allow the sediment in the filtration tower to flow into the sediment receiving tank by opening the sediment transfer valve. At the bottom of the filtration tower, the filter medium with a relatively high specific gravity and large particle size is deposited below the filter medium with a relatively low specific gravity and small particle size. Flows into the sediment receiving tank, and a small-diameter filter medium flows later. Therefore, even if the opening of the filter in the sediment receiving tank is larger than the particle size of the small particle size filter medium, the small particle size filter medium hardly passes through the filter.

  Embodiments of the method and apparatus for treating copper particle-containing water according to the present invention will be described in detail below.

[Copper particle-containing water]
In the present invention, the copper particle-containing water to be treated is copper particle-containing water discharged from a copper product polishing step, a step of processing copper particles as a raw material into a product, and the like. Generally contains copper particles in an SS concentration of about 10 to 1000 mg / L, and the others are wastewater having a pH of about 5 to 8 which is almost pure water. Such copper particles in the water containing copper particles are usually present in the form of copper oxide (Cu ₂ O), and therefore the waste water has a brown color.

  The present invention is effective when the particle size distribution of such copper particle-containing water is particularly wide, it takes too much time for precipitation separation, and there is no suitable sieve for separation by sieving. is there.

[Copper ion]
Although there is no restriction | limiting in particular as copper ion added to copper particle containing water, The thing derived from copper compounds, such as copper sulfate, cupric chloride, copper nitrate, copper carbonate, is used. These are usually added to the copper particle-containing water as a 5 to 25% by weight aqueous solution. Moreover, the copper ion containing waste_water | drain discharged | emitted from a copper plating process, a copper product acid washing process, etc. can also be used as a copper ion supply source. As the copper ions, various copper compounds and wastewater-derived ones may be used alone, or two or more kinds may be mixed and used.

  The amount of copper ion added may be an amount that allows copper particles in copper particle-containing water to settle with sufficient coprecipitation, and also depends on the amount of copper particles in the copper particle-containing water and the sedimentation properties (particle size, etc.). Although it is different, it is preferable that the amount of copper ions added to the copper equivalent of the copper particles in the copper particle-containing water is usually 0.1 to 5 times by weight, particularly about 0.5 to 2 times by weight.

[PH adjustment]
After adding copper ions to copper particle-containing water and mixing, add pH adjuster such as alkali as necessary to adjust pH to 8-10, preferably pH 9-10 to produce copper hydroxide floc At the same time, the copper particles are taken into the floc. Here, in order to incorporate copper particles into the generated floc sufficiently stably, prior to the addition of alkali, the copper particle-containing water and the added copper ions (copper ion-containing water) may be sufficiently stirred and mixed. preferable.

  As described above, the copper particle-containing water is usually a neutral wastewater having a pH of about 5 to 8, and the mixed liquid after adding copper ions to this has a pH of about 5 to 8. An alkali such as sodium (NaOH) is used. Here, if the adjusted pH is too low, the copper ions in the water cannot be sufficiently flocculated as copper hydroxide, and if it is too high, the amount of floc produced is not much different and the amount of alkali added increases and is uneconomical. In addition, it is necessary to adjust the pH by adding an acid for discharging the treated water, which is not preferable.

[Aggregation treatment]
After adding copper ions to the copper particle-containing water and adjusting the pH to 8 to 10, the generated floc is subjected to solid-liquid separation. However, it is preferable to add a flocculant and perform agglomeration before solid-liquid separation.

  As the aggregating agent used in the aggregating treatment, organic polymer aggregating agents, particularly sodium polyacrylate, partially hydrolyzed polyacrylamide, and the like are preferable, and one or more of these can be used.

  The addition amount of the flocculant is usually about 0.1 to 5 mg / L, although it varies depending on the water quality of the copper particle-containing water to be treated and the adjusted pH.

  By aggregating, the floc in water can be increased to about 1-10 mm, and solid-liquid separability can be improved.

[Solid-liquid separation process]
As described above, the copper hydroxide flock incorporating copper particles has improved sedimentation properties compared to copper particles in copper particle-containing water, but further, those having poor sedimentation properties are also mixed, so that the present invention. Then, such solid-liquid separation of floc is preferably performed using a filtration apparatus having a floating filter medium layer, preferably a floating filtration apparatus shown in FIGS.

  When solid-liquid separation is performed using such a floating filtration device, if the water flow LV is too large, flocs do not settle and most of the flocs are trapped in the floating filter media layer, resulting in a difference in the floating filter media layer. There is a risk that the pressure will rise rapidly and become unfilterable. In addition, the flocs captured by the floating filter medium layer originally have a filter medium function. However, if the water flow LV is too large, the flocs are broken, the SS trapping ability is deteriorated, and the quality of treated water is lowered. Since flocs are less likely to settle to the lower part of the filtration tower, the concentration of separated sludge is low. Accordingly, the water flow LV is preferably 25 m / hr or less. From the viewpoint of filtration efficiency, the water flow LV is preferably 7 m / hr or more, particularly preferably 10 to 20 m / hr.

  However, the solid-liquid separation is not limited to the filtration device having a floating filter medium layer, and can be performed using a combination of a floating separation device, a precipitation tank and a filtration device having a fixed filtration layer, or the like.

  Sludge obtained by solid-liquid separation is dehydrated by a dehydrator such as a filter press, screw press, or belt press, and then subjected to a copper recovery process. On the other hand, the separated water is further subjected to post-treatment such as pH adjustment as necessary, and then recovered as industrial water such as discharged water or field work water.

[Processing flow]
FIG. 1 shows an example of a processing flow suitable for implementing the present invention.

  The raw water copper particle-containing water is introduced into the mixing tank 61, and copper ions, for example, copper sulfate-containing waste water, a copper compound aqueous solution, and the like are added thereto and stirred and mixed for about 5 to 10 minutes. The mixed water from the mixing tank 61 is introduced into the pH adjusting tank 62, and an alkali such as NaOH is added to adjust the pH to 8 to 10, preferably 9 to 10. In the pH adjusting tank 62, it is preferable to perform stirring and mixing for about 5 to 15 minutes.

  After the polymer flocculant is added, the pH-adjusted water from the pH-adjusting tank 62 is solid-liquid separated by the filtering device 63, and the separated water is discharged out of the system through the treated water tank 64 and discharged.

  On the other hand, the separated sludge is dewatered by the dehydrator 66 through the sludge tank 65, and the dewatered cake is discharged out of the system and sent to the copper recovery process.

  FIG. 1 shows an example of an embodiment of the present invention, and the present invention is not limited to the illustrated embodiment as long as the gist thereof is not exceeded.

  For example, a coagulation tank may be provided between the pH adjustment tank 62 and the filtration apparatus 63, and a part of the sludge separated by the filtration apparatus 63 is returned to the pH adjustment tank 62 in order to obtain a seed crystal action. Alternatively, this sludge may be mixed with an alkali and added to the pH adjusting tank 62.

[Filtration device with floating filter media layer]
A filtration apparatus having a floating filter medium layer suitable as a floc solid-liquid separation means in the present invention will be described below with reference to FIGS.

  FIG. 2 is a system diagram showing an example of a flotation filtration apparatus suitable as a filtration apparatus used for floc solid-liquid separation in the present invention, and FIG. 3 is a horizontal sectional view of the filtration tower.

This floating filtration apparatus introduces raw water in a raw water tank 1 into a filtration tower 10 via a pipe 2, a valve V ₁ , a pump P, a pipe 3, a valve V ₂ and a pipe 4, and a filtration layer made of a floating filter medium. 13, and is taken out as filtered water from the water collection pipe 14 and the pipe 30, and this filtered water is led to the filtered water tank 33 through the valve V ₃ and the pipe 31.

In addition, in order to guide the water in the filtered water tank 33 to the pipe 2, the pipe 5 provided with the valve V ₄ joins the pipe 2, and the pipe 6 branched from the pipe 3 passes through the valve V ₅ and the pipe 8. And connected to the vicinity of the top of the filtration tower 10.

  The filtration tower 10 has a cylindrical shape except for the vicinity of the upper end portion and the lower end portion, and is installed with the cylinder axis direction being the vertical direction. A water collection pipe 14 is provided at the top of the filtration tower 10. Further, a filtration layer 13 made of a floatable filter medium is formed in the upper part of the filtration tower 10. The filtration layer 13 includes a filtration layer (hereinafter sometimes referred to as a “small particle size layer”) 11 made of a small particle size filter material and a filtration layer (hereinafter referred to as “large particle size filter material” made of a large particle size filter material below the filter layer 13. It may be referred to as a “particle size layer.”)

  The specific gravity of the large particle size filter medium and the small particle size filter medium is equal to or less than the specific gravity of the raw water, and the specific gravity is preferably smaller than the specific gravity of the raw water so as to surely float. The specific gravity of the small particle size filter medium is smaller than the specific gravity of the large particle size filter medium, and as described later, the specific gravity of the small particle size filter medium so that the small particle size filter medium floats before the large particle size filter medium after backwashing. Is smaller than the specific gravity of the large particle size filter medium. For example, the specific gravity of the small particle size filter medium is preferably 0.08 to 0.30, the specific gravity of the large particle size filter medium is preferably 0.50 to 0.95, and the specific gravity of the small particle size filter medium is particularly preferably 0.10 to 0. .15, the specific gravity of the large particle size filter medium is preferably 0.85 to 0.95.

  The particle size of the large particle size filter medium and the small particle size filter medium is appropriately selected according to the particle size of the suspended solids in the raw water and the required treated water quality. A filter medium having a particle size of about 0.1 to 0.6 mm, particularly about 0.3 to 0.5 mm is preferable.

  Various materials such as synthetic resins such as polyethylene, polypropylene and polystyrene, and inorganic foams can be used as the material for the floatable filter medium. Among them, foamed synthetic resins such as expanded polystyrene are preferred.

  The large-diameter filter medium and the small-diameter filter medium are preferably subjected to a surface hydrophilization treatment such as carrying a surfactant or polyvinyl alcohol on the surface. Thereby, at the time of standing after backwashing mentioned below, aggregation of a large particle size filter material and a small particle size filter material is prevented, and a large particle size layer and a small particle size layer can be formed appropriately.

  The filling amount of the large particle size filter medium and the small particle size filter medium is set such that the lower surface of the filter layer 13 is slightly lower than the connection portion of the pipe 4. Further, the interface between the small particle size layer 11 and the large particle size layer 12 is set higher than the connection portion of the pipe 4 by a required distance.

  As shown in FIG. 3, the raw water introduction pipe 4 is connected so that the introduction direction of the raw water introduced into the filtration tower 10 is a swirl direction in the horizontal section of the cylindrical filtration tower 10. Preferably, the pipe 4 is connected to the cylindrical filtration tower 10 in a tangential direction.

A pipe 21 for taking out a mixture of the floatable filter medium and raw water is connected to the side surface of the filtration tower 10 slightly below the lower part of the filtration layer 13. The pipe 21 is connected to a position downstream of the raw water pump P in the pipe 2. Valve V ₆ is provided in the pipe 21.

The filtered water extraction pipe 30 is provided with an air release valve V ₇ for communicating the inside of the pipe 30 with the atmosphere.

A pipe 32 is branched from the pipe 30, and the pipe 32 is led to the sludge storage tank 60 through a valve V ₈ .

  The lower part of the filtration tower 10 has a tapered shape that decreases in diameter toward the lower end.

A pipe 41 for discharging the settled sludge and the filter medium is provided at the lower end of the filter tower 10, and a valve V ₉ is provided in the pipe 41. Sludge and filter medium discharged through the pipe 41 are introduced into the sediment receiving tank 50. The sediment receiving tank 50 is partitioned into an upper chamber 52 and a lower chamber 53 by a substantially inverted conical filter 51, and sludge and filter medium are introduced into the upper chamber 52. The size of the opening of the filter 51 is smaller than that of the large particle size filter medium, but larger than that of the small particle size filter medium. The sediment receiving tank 50 is preferably provided at a position below the lower end of the filtration tower 10 because the sediment easily moves from the filtration tower 10 to the sediment receiving tank 50.

The upper end of the sediment receiving tank 50 is connected via a pipe 54 for discharging the filter medium, a valve V ₁₀ and a pipe 55.
Then, it is connected to the raw water introduction pipe 3. The pipe 55 obliquely crosses the pipe 3 so as to gradually approach the pipe 3 toward the downstream side of the pipe 3. For this reason, when water flows from the pump P in the pipe 3, the water in the pipe 55 is sucked into the pipe 3 by the ejector action with respect to the vicinity of the pipe 3 and the pipe 55. However, instead of making the pipe 55 obliquely cross the pipe 3, an ejector may be provided in the pipe 3, and the pipe 55 may be connected to the ejector.

A pipe 56 with a valve V ₁₁ branches from the pipe 54.

A pipe 57 with a valve V ₁₂ is inserted into the sediment receiving tank 50 so that the sludge is discharged from the upper chamber 52 to the sludge storage tank 60. The pipe 57 is raised upward from the center of the filter 51.

A pipe 58 with a valve V ₁₃ is connected to the bottom of the sediment receiving tank 50 so that the sludge is discharged from the lower chamber 53 to the sludge storage tank 60.

In this embodiment, a pipe 59 with a valve V ₁₄ is connected to the sediment receiving tank 50 so as to blow air into the lower chamber 53.

  The sludge in the sludge storage tank 60 can be sent to a sludge treatment process via a sludge extraction pipe (not shown) having a pump.

  Next, an operation for performing a levitation filtration operation using the levitation filtration apparatus configured as described above will be described.

First step: water filling First, as a preparatory operation for the filtration operation, the valves V ₁ , V ₂ , V ₇ , V ₉ and V ₁₀ are opened, and the other valves (V _{3 to} V ₆ , V ₈ , V _{11 to} V ₁₄ are opened. ) Is closed and the pump P is driven. By driving the pump P, the raw water in the raw water tank 1 is introduced into the filtration tower 10 through the pipe 2, 3, 4, air filtration tower 10 is released from the valve V _7, filtration tower 10 is filled with water. Further, after a part of the water in the filtration tower 10 is introduced into the sediment receiving tank 50 through the pipe 41 and the inside of the sediment receiving tank 50 is filled with water, excess raw water is supplied through the pipe 55. And returned to the pipe 3. Incidentally, in the initial water filling into the sediment receiving tank 50, the valve V ₁₀ closed, the valve V ₁₁ is opened, air sediment receiving tank 50 may be released from the pipe 56.

Second step: Filter media stirring Next, the valves V ₂ , V ₅ , V ₆ , V ₉ , V ₁₀ are opened, and the other valves V ₁ , V ₃ , V ₄ , V ₇ , V ₈ , V _{11 to} V ₁₁ -V. ₁₄ is closed and the pump P is operated. Thereby, the water in the filtration tower 10 circulates through the pipes 3, 4, 6 and the pipes 21, 41, 55, and the entire filter medium of the filter layer 13 is stirred.

Third step: Calm Next, the pump P is stopped, the valves V ₂ , V ₉ , and V ₁₀ are opened, and all other valves are closed. Thereby, the water in the filtration tower 10 is settled, and the filtration layer 13 including the upper small particle diameter layer 11 and the lower large particle diameter layer 12 is formed in the filtration tower 10.

4th process: Filter material layer washing | cleaning Prior to starting filtration operation, the washing process of the filtration layer 13 is performed. In this cleaning process, the valves V ₁ , V ₂ , V ₆ , V ₈ , V ₉ , V ₁₀ are opened, the other valves are closed, and the pump P is driven. Thereby, the raw water in the raw water tank 1 is supplied to the pipes 3 and 4, the filtration layer 13, and the pipe 32.
It flows in order and is discharged to the sludge storage tank 60. If this water flow is continued, the quality of the effluent water of the filtration layer 13 will gradually become better. Therefore, when the quality of the effluent water becomes better than specified, this washing step is terminated.

  During this cleaning operation, the lower part of the large particle size layer 12 swirls and flows with the inflow water from the pipe 4 to form a swirling fluidized bed 12a. Further, a part of the water in the filtration tower 10 is sucked into the pipe 3 and circulated through the pipe 21, the pipe 41, the sediment receiving tank 50, and the pipe 55. The same applies to the fifth step described later.

Step 5: passing water Therefore, the valve _{V 8} from the state of the fourth step closed, the valve _{V 3} opened _(i.e., the _{V 1 ~V 3, V 6,} V 9, V 10 open, the other valve The pump P is driven. Thereby, the raw water in the raw water tank 1 flows in the order of the pipes 3 and 4, the filtration layer 13 in the filtration tower 10, and the pipes 30 and 31, and the filtered water is introduced into the filtered water tank 33.

  That is, by driving the pump P, the raw water in the raw water tank 1 is introduced into the filtration tower 10 via the pipes 2, 3, and 4 in the swirling direction, and the large particle size below the large particle layer 12 Part of the filter medium is introduced into the pipe 2 through the pipe 21 together with water, and further circulated through the pump P and the pipe 3. Thus, during the floating filtration operation, the swirling fluidized bed 12a is formed in the lower part of the large particle size layer 12 by the introduced raw water and the circulating floating filter medium. The raw water is filtered through the large particle size layer 12 and the small particle size layer 11 including the swirling fluidized bed 12 a, and then sent to the filtered water tank 33 from the pipes 30 and 31 through the water collecting pipe 14. During this filtration operation, since the lower part of the filtration layer 13 forms the swirling fluidized bed 12a, clogging of the floating filter medium at the lower part of the filtration layer 13 is suppressed, and even if the washing frequency of the filtration layer 13 is significantly reduced, The filtration operation can be continued continuously for a long time with low pressure loss. Of the filtration layer 13, clogging is prevented because the lower portions where clogging is likely to occur are the fluidized bed 12 a and the large particle size layer 12 made of a large particle size filter medium. Moreover, since the upper part of the filtration layer 13 is the small particle diameter layer 11, highly accurate filtration is possible, and thereby high-purity filtered water can be obtained.

  As described above, when the raw water is introduced in the swirling direction, the swirling fluidized bed 12a of the large particle size filter medium is formed at the lower part of the filter layer 13. At this time, the circulating and floating filter medium is also added to the swirling fluidized bed 12a together with the raw water. Since it is introduced, the filter medium collides with the lower surface of the filtration layer and disturbs the lower portion of the filtration layer, facilitating the formation and renewal of the swirling fluidized bed 12a. Moreover, the collision of the filter medium peels off the deposits adhering to the filter medium, contributing to suppression of clogging. Furthermore, since the fixed layer formed of the large-diameter filter medium has an inverted conical shape due to the swirling flow, the area of the lower surface of the filter layer that is most likely to be clogged increases. Therefore, this floating filtration device can also filter raw water having a very high SS concentration of, for example, SS 1000 mg / L or more.

  And by forming the swirl flow, the water in the filtration tower 10 below the filter layer also swirls, and the relatively heavy suspended matter contained in the raw water, the filter cake separated from the filter medium by the swirl flow The cyclone action collects in the vicinity of the central portion of the filtration tower 10 and tends to settle, and settles to the bottom of the filtration tower 10. The sludge that has settled at the bottom of the filtration tower 10 is discharged from the pipe 41 to the sediment receiving tank 50.

  In addition, although the example which circulates a floatable filter medium using the pump P for raw | natural water introduction was shown, depending on conditions, such as the magnitude | size of the filtration tower 50, the pump for filter medium circulation was installed and swirl flow was further strengthened. You may wake up.

When withdrawing the sludge collected in the bottom sediment receiving tank 50 during the flight filtration operation, the sludge valve V ₁₃ is opened via a pipe 58 extracting the sludge storage tank 60.

  As described above, if the filtration operation is continued for a long period of time, the filtration pressure loss gradually increases. Therefore, the filtration layer 13 is back-washed.

  Prior to this backwashing, it is preferable to first calm down as the valve state of the third step. This is to return the small-diameter filter medium that may be mixed in the lower part of the filter layer 13 to the upper side of the filter layer 13 as much as possible, so that the small-diameter filter medium does not flow out to the sediment receiving tank 50 in the next sludge process. Because. However, the calming step may be omitted prior to this backwashing.

Step 6: Waste mud With the pump P stopped, the valves V ₇ , V ₉ , V ₁₃ are opened and the other valves are closed. Thereby, the water in the filtration tower 10 is discharged to the sludge storage tank 60 through the pipe 41, the sediment receiving tank 50 and the pipe 58, and the sludge deposited in the filtration tower 10 and the sediment receiving tank 50 is sludge storage tank. It is discharged to 60. To the filtration tower 10 air is introduced through a valve V ₇ from the top.

Seventh step: water filling Next, the valves V ₂ , V ₄ , V ₇ , V ₉ , V ₁₀ are opened, the other valves are closed, the pump P is driven, and the filtration tower 10 is filtered with filtered water in the filtered water tank 33. Satisfy inside. Air filtration tower 10 is discharged through a valve V ₇ to the atmosphere.

Eighth step: backwashing Therefore, the valves V ₄ , V ₅ , V ₆ , V ₉ , V ₁₀ are normally opened, the other valves are closed, and the pump P is driven. Thereby, water is extracted from the lower part and the bottom part of the filtration tower 10 through the pipe 21 and the pipe 41, the sediment receiving tank 50, and the pipe 55, respectively, and this water is supplied to the upper part of the filtration tower 10 through the pipe 8. The water in the filter tower 10 is circulated and the filter layer 13 is backwashed. Incidentally, intermittently to open the valve V ₈ or V _13, a portion of the water through the pipe 32 or 58 is discharged into the sludge storage tank 60 during backwash. Thus, when discharging water to the sludge storage tank 60, the water in the filtration water tank 33 is replenished to the filtration tower 10 through the pipes 5, 3, 6, and 8.

Opening and closing the valves V _8, the water collecting pipe 14 by the impact at that time is also cleaned.

  In the step of circulating the water in the filtration tower 10 and backwashing in this way, the large particle size filter medium and the small particle size filter medium are stirred and mixed. At this time, the filter media collide with each other, and the foreign matter attached to the filter media is peeled off. In particular, the filter medium includes a large particle size filter medium having a large specific gravity. Since the large particle size filter medium has a large impact force, the cleaning effect is greatly improved as compared with the case where only the small particle size filter medium is provided.

Ninth step: Filter cleaning Thereafter, the pump P is stopped, the valves V ₁₁ , V ₁₂ and V ₁₄ are opened, and the other valves are closed. Further, air is blown into the sediment receiving tank 50 through the pipe 59. Thereby, the inside of the filter 51 and other sediment receiving tank 50 is washed. The water mixed with air is discharged through the pipe 57. At this time, even if the small-diameter filter medium is wound around the sediment and falls to the lower chamber 53, the sediment is peeled off from the small-diameter filter medium by the air blowing effect, and the small-diameter filter medium is filtered. Since it can be returned to the filtration tower 10 through 51, there is no concern that the small-diameter filter medium is discharged into the sludge storage tank 60. Although provided a valve V ₁₄ with the pipe 59 as a means for supplying a gas to precipitate the receiving tank 50, or in conjunction with the pipe 59 instead of the pipe 59, even if the vibrator attached to sediment receiving tank 50 Good. In this case, the sediment is peeled off from the small particle size filter medium by the effect of the vibrator.

Tenth step: Waste mud Then, the valves V ₇ , V ₉ , V ₁₃ are opened, and the other valves are closed. Thereby, the water in the filtration tower 10 is discharged to the sludge storage tank 60 through the pipe 41, the sediment receiving tank 50, and the pipe 58, and the sludge in the filtration tower 10 and the sediment receiving tank 50 is also discharged to the sludge storage tank 60. The

  Thereafter, preferably, the series of steps from the sixth step to the tenth step is repeated 1 to 5 times.

  Then, it returns to a 1st process, moves to the water flow operation of a 5th process through each process of a 2nd process-a 4th process, and performs a filtration operation.

  Hereinafter, the present invention will be described in more detail with reference to experimental examples and examples.

Experimental example 1
An experiment was conducted to examine the sedimentation property using the water-containing copper particle-containing water shown in Table 1 discharged from the buffing process of the copper product.

This copper particle-containing water is a liquid containing brownish brown granular copper, and the color indicates that copper is present in the state of copper (I) Cu ₂ O. The copper powder in the copper particle-containing water settles for a long time, but if the particle size of the copper particles does not settle due to gusset, it does not settle indefinitely.

<No. 1, 2>
The treatment was performed by adding the water-containing copper sulfate-containing waste water shown in Table 1 discharged from the washing step of washing the copper disk with sulfuric acid as a copper ion supply source.

  After adding copper sulfate-containing wastewater to the copper particle-containing water so as to be the amount shown in Table 2 as the amount of Cu-converted addition, the mixture is stirred for 1 minute, then adjusted to the pH shown in Table 2 by adding NaOH, and stirred for 3 minutes. did. Thereafter, an anionic polymer flocculant “PA-331” manufactured by Kurita Kogyo Co., Ltd. was added as a polymer flocculant in the amount shown in Table 2, and the mixture was stirred for 1 minute and allowed to stand, and 90% of the flock settled. The time required for this was investigated, and the results are shown in Table 2.

<No. 3>
A 1 wt% aqueous solution of copper sulfate pentahydrate was used in place of the copper sulfate-containing waste water, and the addition amount and adjusted pH were as shown in Table 2 above. The same treatment as in 1 was performed, and the results are shown in Table 2.

<No. 4>
The copper particle-containing water was allowed to stand as it was, and the sedimentation time was examined. The results are shown in Table 2.

<No. 5>
The amount of polymer flocculant shown in Table 2 was added to the copper particle-containing water and the mixture was allowed to stand and the sedimentation time was examined. The results are shown in Table 2.

<No. 6,7>
No. 2 except that ferric chloride was added to the copper particle-containing water in place of the copper sulfate-containing wastewater. The same treatment as in 1 was performed, and the results are shown in Table 2.

  From Table 2, it can be seen that the copper particle-containing water has poor sedimentation, and as such, the copper particles cannot settle, and even when a polymer flocculant is added, the sedimentation is not improved (No. 4, 5). .

  Addition of ferric chloride improves sedimentation, but it is not sufficient, and in this case, there is a problem that iron is mixed into the separated sludge (No. 6, 7).

  On the other hand, it can be seen that by adding copper ions, the sedimentation property is remarkably improved and the floc can be sedimented in a sedimentation time of about 1 minute (No. 1 to 3).

  In addition, the No. which added the copper sulfate containing waste water and the polymer flocculent in large quantities. In No. 2, the sedimentation time was fast, but the sedimentation sludge was in a blistering state. This is presumably because the excessively added polymer flocculant remained in the liquid.

Example 1
The copper particle-containing water shown in Table 1, copper sulfate-containing waste water as a copper ion supply source, and an anionic polymer flocculant “PA-331” manufactured by Kurita Kogyo Co., Ltd. as a polymer flocculant are shown in FIG. Processed with flow. As the filtration device, the floating filtration device shown in FIGS. The specifications of this floating filtration device are as follows.

<Floating filter device>
Filtration tower 10: cylindrical shape having a diameter of 300 mm × height of 1000 mm Filter medium layer height: large particle size layer (12, 12a) 250 mm
Small particle size layer (11) 250mm
Sediment receiving tank: cylindrical shape with diameter 150mm x height 600mm

  After adding copper sulfate-containing wastewater to the copper particle-containing water in the mixing tank 61 so that the added amount in terms of copper ion is 50 mg-Cu / L, the mixture is stirred and mixed for 1 minute, and then NaOH is added in the pH adjusting tank 62 to 3 After stirring and mixing for a minute, the pH was adjusted to 9.26, and then 0.4 mg / L of the polymer flocculant was line-injected, followed by solid-liquid separation with a flotation filter. The water flow LV at this time was 10 m / hr.

  As a result, more than half of the flock settled in the floating filtration device, and the remainder was supplied to the floating filter media layer and captured. The time-dependent change of the differential pressure in the floating filtration device at this time was as shown in FIG. Further, the water quality of the obtained treated water (the filtered water of the floating filtration device) and the concentration of the separated sludge (sludge accumulated in the sediment receiving tank of the floating filtration device) were as shown in Table 3.

Example 2
In Example 1, it processed similarly except having set the water flow LV of the floating filtration apparatus to 20 m / hr. The time-dependent change of the differential pressure in the floating filtration device at this time was as shown in FIG. In addition, the quality of the treated water and the sludge concentration were as shown in Table 3.

  From the results of Examples 1 and 2, the following can be understood.

  By adjusting the pH to alkaline by adding copper sulfate-containing wastewater to copper particle-containing water, the copper particles can be taken into the floc of copper hydroxide to improve sedimentation, and by solid-liquid separation, Although treated water with good water quality can be obtained, the flow rate LV of the flotation filter device at that time affects the treatment efficiency, and in Example 2 performed at LV 20 m / hr, most of the flocs do not settle and the flotation filter medium Since it was supplied to the bed, the differential pressure increased rapidly and filtration became impossible. Moreover, the sludge concentration was low, and a slight outflow of SS into the treated water was observed.

  On the other hand, in Example 1 treated with water flow LV 10 m / hr, more than half of the flock settled and the remainder was supplied to the floating filter media layer, so the increase in the differential pressure was not so great, and the operation was more than 30 minutes. It was possible to continue.

  Moreover, the sludge is also consolidated at a high concentration, which is advantageous for the subsequent dehydration treatment, and the SS concentration of the treated water is low, so that treated water with good water quality is obtained.

It is a systematic diagram which shows embodiment of the processing method and apparatus of the copper particle containing water of this invention. It is a systematic diagram which shows an example of the filtration apparatus suitable for the solid-liquid separation of the floc in this invention. It is a horizontal sectional view of the filtration tower of FIG. 3 is a graph showing a change with time of the filtration differential pressure of the floating filtration device in Example 1. FIG. It is a graph which shows a time-dependent change of the filtration differential pressure | voltage of the floating filtration apparatus in Example 2. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Raw water tank 10 Filtration tower 11 Small particle size layer 12 Large particle size layer 12a Fluidized bed 13 Filtration layer 33 Filtration water tank 50 Sediment receiving tank 60 Sludge storage tank
61 Mixing tank 62 pH adjustment tank 63 Filtration device 64 Treated water layer 65 Sludge tank 66 Dehydrator

Claims (6)

  It is characterized in that copper ions are added to and mixed with copper particle-containing water, the pH is adjusted to 8 to 10 to produce copper hydroxide floc, copper particles are taken into the floc, and then solid-liquid separation is performed. To treat copper-containing water.   In Claim 1, the said solid-liquid separation is performed using the filtration apparatus which has a floating filter material layer, The processing method of the copper particle containing water characterized by the above-mentioned. The filter device according to claim 2,
A flotation filtration device in which a filtration layer is formed by a flotation filter medium in a cylindrical filtration tower having a cylinder axis direction as a vertical direction,
Raw water introduction pipe for introducing raw water into the lower part of the filtration layer in a swirling direction to generate swirl flow in the lower part of the filtration layer;
A filter medium circulating means for taking out a part of the floating filter medium from the lower part of the filter layer and introducing it again into the lower part of the filter layer;
A sediment receiving tank for separating the floating filter medium from the floating filter medium-containing sediment, wherein the floating filter medium-containing sediment is introduced from the bottom of the filtration tower;
A flotation filter medium returning means for guiding the flotation filter medium from which the solid content has been separated in the sediment receiving tank to the raw water introduction pipe;
With
The floating filter return means has an ejector-type suction means provided in the raw water introduction pipe, and the floating filter medium is sucked from the sediment receiving tank by the ejector-type suction means and returned to the raw water introduction pipe. A method for treating water containing copper particles, characterized in that:   Mixing means for adding and mixing copper ions to copper particle-containing water, and adjusting the pH of the mixed water obtained by the mixing means to 8 to 10 to produce copper hydroxide flocs, and copper particles in the flocs An apparatus for treating copper particle-containing water, comprising: pH adjusting means for taking in water; and means for solid-liquid separation of water from the pH adjusting means.   5. The treatment apparatus for water containing copper particles according to claim 4, wherein the solid-liquid separation means is a filtration device having a floating filter medium layer. The filter device according to claim 5,
A flotation filtration device in which a filtration layer is formed by a flotation filter medium in a cylindrical filtration tower having a cylinder axis direction as a vertical direction,
Raw water introduction pipe for introducing raw water into the lower part of the filtration layer in a swirling direction to generate swirl flow in the lower part of the filtration layer;
A filter medium circulating means for taking out a part of the floating filter medium from the lower part of the filter layer and introducing it again into the lower part of the filter layer;
A sediment receiving tank for separating the floating filter medium from the floating filter medium-containing sediment, wherein the floating filter medium-containing sediment is introduced from the bottom of the filtration tower;
A flotation filter medium returning means for guiding the flotation filter medium from which the solid content has been separated in the sediment receiving tank to the raw water introduction pipe;
With
The floating filter return means has an ejector-type suction means provided in the raw water introduction pipe, and the floating filter medium is sucked from the sediment receiving tank by the ejector-type suction means and returned to the raw water introduction pipe. An apparatus for treating copper particle-containing water.

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