JP5257040B2 - Water treatment method - Google Patents

Description

  The present invention relates to a water treatment method.

  In a manufacturing process of an aqueous dispersion in a manufacturing factory of a toner for developing an electrostatic charge image (hereinafter sometimes simply referred to as “toner”), water containing a coloring component may be generated. These waters often contain dispersants such as surfactants in order to increase the dispersibility of pigments, etc. in addition to pigments and dyes that are coloring components. The oxygen demand (COD) is large and cannot be discharged into rivers or sewers in this state. Therefore, these waters are reused after being treated at a water treatment facility in the factory, or are discharged to the outside after being treated.

  In particular, as a method for producing toner, various chemical toner production methods such as emulsion polymerization method, suspension polymerization method, dissolution suspension method and the like have been developed and implemented instead of conventional kneading and pulverization methods. . For example, in the emulsion polymerization method, a resin dispersion formed by emulsion polymerization of a polymerizable monomer of a binder resin, a colorant, a release agent, and a charge control agent as necessary in the presence of a surfactant, While stirring and mixing in an aqueous solvent, toner particles that are colored resin particles having a predetermined particle size, particle size distribution, shape, structure, etc. are produced by agglomeration and heat fusion. In some cases, a surfactant-containing liquid containing a surfactant such as a colorant dispersion, a release agent dispersion, an emulsion aqueous solution, and apparatus cleaning water may be generated.

  Usually, as a general water treatment, a coagulation sedimentation treatment is often used. As described in Non-Patent Document 1, pages 141 to 153, the coagulation sedimentation treatment is a solid-liquid separation operation most commonly used in the field of water treatment and is widely used. The coagulation sedimentation treatment is a treatment method in which flocs (coarse particles generated by aggregation) are generated by adding a flocculant to raw water, and solids and liquids are separated by precipitating the flocs due to the specific gravity difference between water and flocs. . The flocs thus separated as solids are treated as sludge for industrial waste, and the water from which the solids have been separated can be reused or discharged into rivers, sewers, etc., with reduced chemical oxygen demand. The sludge after the solid-liquid separation is often dehydrated as it is with a pressure filtration dehydrator. The pressure filtration dewatering device is a dewatering device that is most commonly used in the field of water treatment, as described on page 182 of Non-Patent Document 1.

  Patent Document 1 discloses that in a wastewater treatment method for solid-liquid separation of organic pollutant-containing wastewater, a part of the generated sludge is returned to the treated raw water side and circulated so that the final treatment of sludge is easy. A method is described.

  Patent Document 2 describes a method of performing pressure flotation separation in the treatment of emulsion wastewater.

  Patent Document 3 describes a treatment method that uses an inorganic flocculant, a polymer flocculant, and an organic flocculant for wastewater containing a surfactant and that is low in running cost and easy to manage.

JP-A-7-136408 Japanese Patent Laid-Open No. 9-225474 JP 2006-7208 A Supervised by the Ministry of International Trade and Industry, Environmental Location Bureau, “Fiveth Pollution Prevention Technology and Regulations (Water Quality)”, published in 2001, pages 141-153, page 182

  The present invention is a water treatment method for efficiently treating raw water containing a surfactant generated from a manufacturing process of an electrostatic charge image developing toner and reducing the amount of aggregating agent used and the amount of sludge generated.

The present invention comprises a resin particle dispersion liquid in which resin particles are dispersed, a colorant dispersion liquid in which a colorant is dispersed, and a release agent dispersion liquid in which a release agent is dispersed to form an agglomerated particle; A stop step of adjusting the pH in the agglomeration system to stop the agglomeration growth of the agglomerated particles, and a fusion step of fusing the agglomerated particles by heating to a temperature equal to or higher than the glass transition temperature of the resin particles. A raw water containing a surfactant, which is generated from the production process of the toner for developing an electrostatic charge image, containing a surfactant, and an ethylenediamine disuccinic acid addition step of adding ethylenediamine disuccinic acid to the raw water, and raw water containing ethylenediamine disuccinic acid A flocculant is added to the flocs, a floc formation process for forming flocs from the flocculant reacted in the reaction step, and a floc separated from the flocs and the separation liquid. A separation step, a water treatment method comprising.

  According to the first aspect of the present invention, compared with the case where ethylenediamine disuccinic acid is not used, the raw water containing the surfactant generated from the production process of the toner for developing an electrostatic charge image is efficiently treated and agglomerated. Reduce the use of chemicals and sludge generation.

  Embodiments of the present invention will be described below. This embodiment is an example for carrying out the present invention, and the present invention is not limited to this embodiment. Here, the water treatment method according to the embodiment of the present invention will be described using a coagulation sedimentation process as an example. The water treatment method according to the present embodiment is not particularly limited as long as raw water containing a surfactant, which is generated from the manufacturing process of the toner for developing an electrostatic charge image, is treated.

  According to the results examined by the present inventors, it contains a surfactant aqueous solution, a colorant dispersion, a release agent dispersion, an emulsion aqueous solution, an apparatus cleaning water, etc., generated from the toner production process. In the surfactant-containing liquid, due to the action of the surfactant, the settling time in the coagulation sedimentation process is prolonged, and the amount of the inorganic coagulant used for coagulation sedimentation, such as ferric chloride, is increased, As a result, the amount of the aggregated precipitate, that is, a large amount of sludge to be treated as industrial waste may be generated. This is because an amount of an inorganic salt such as ferric chloride used as an inorganic flocculant undergoes charge neutralization reaction with the surfactant contained in the surfactant-containing liquid, and acts as a flocculant. This is thought to be because of the inhibition.

  Furthermore, the inventors of the present invention can form a surfactant aggregate, and if the surface area of the surfactant is reduced, the amount of the surfactant that neutralizes and reacts with the flocculant due to the precipitation of the surfactant by the flocculant. Thought to reduce. That is, since the amount of the flocculant neutralized by the surfactant is reduced, the amount of the flocculant to be used is reduced, and the amount of generated sludge is reduced.

  Therefore, as a result of intensive studies, the present inventors, in the raw water containing surfactants generated from the toner production process, in the previous process of adding a flocculant to the raw water, for example, in the previous process It has been found that the addition of ethylenediamine disuccinic acid to the raw water reduces the amount of flocculant used and reduces the amount of sludge generated. By forming a colloidal complex by coordinating ethylenediamine disuccinic acid with a surfactant, the surface area of the surfactant is reduced, the amount of coagulant used is reduced, and the amount of sludge generated is considered to be reduced.

  In addition, flocs are formed in the thus obtained agglomeration reaction solution, and then the precipitates (sludge slurry) in which the flocs are concentrated by centrifugation using a centrifugal separator (decanter, perforated plate centrifugal separator, etc.) After the separation process to separate into the separated liquid, the obtained sludge slurry is separated and removed using a pressure filter (filter press, pressure leaf filter, pressure nutsche etc.) etc. As a result, it was found that the solid-liquid separation time is significantly shortened.

  By combining the above flocculation treatment and separation treatment by centrifugation, the amount of flocculant used in water treatment and the amount of sludge generated are greatly reduced, and the time required for water treatment is also shortened, so productivity is also improved. Greatly improved.

[Water treatment method]
Although the water treatment method which concerns on this embodiment is demonstrated concretely below using drawing, it is not limited to this.

  FIG. 1 shows a schematic configuration of an example of a water treatment apparatus according to an embodiment of the present invention, and the configuration will be described. As shown in FIG. 1, a water treatment apparatus 1 that is an example of a water treatment apparatus according to this embodiment includes a raw water tank 10, a reaction tank 12, a coagulation tank 14, a coagulation sedimentation tank 16, and a biological treatment tank 18. And a post-precipitation tank 20, a sand filtration device 22, an activated carbon filtration adsorption device 24, a sludge concentration device 26, and a dehydration device 28. The configuration of the water treatment apparatus 1 in FIG. 1 is an example, and the present invention is not limited to this. Also,

  In the water treatment apparatus 1 of FIG. 1, the raw water tank 10, the reaction tank 12, the coagulation tank 14, the coagulation sedimentation tank 16, the biological treatment tank 18, the post-precipitation tank 20, the sand filtration apparatus 22, and the inlet and outlet of the activated carbon filtration adsorption apparatus 24. Are connected in series via a pipe or the like. The inlet of the sludge concentrator 26 is connected to the lower part of the coagulation sedimentation tank 16 and the lower part of the post-precipitation tank 20 via a pipe and the like, and the outlet of the sludge concentrator 26 is connected to the inlet of the dehydrator 28 and the pipe etc. It is connected. As addition means for adding ethylenediamine disuccinic acid, the addition pipe is connected to the raw water tank 10 via a pump or the like, and as the flocculant addition means, the flocculant addition pipe is connected to the reaction tank 12 and the aggregation tank 14 via a pump or the like. It may be connected. Agitation means such as a stirring blade may be installed in the raw water tank 10, the reaction tank 12, and the aggregation tank 14.

  The operation of the water treatment method and the water treatment apparatus 1 according to this embodiment will be described.

  Raw water containing a surfactant generated from the toner manufacturing process (hereinafter sometimes simply referred to as “raw water”) is temporarily stored in the raw water tank 10 and is stirred in the raw water tank 10 by stirring means such as a stirring blade. However, ethylenediamine disuccinic acid or an ethylenediamine disuccinic acid-containing solution containing ethylenediamine disuccinic acid is added by a pump or the like (ethylenediamine disuccinic acid addition step). Thereafter, the ethylenediamine disuccinic acid-containing raw water containing ethylenediamine disuccinic acid is fed to the reaction tank 12. Ethylenediamine disuccinic acid may be added before the addition of the flocculant, and there is no particular limitation on the mode of addition. For example, you may add in piping etc. which connect the raw | natural water tank 10 and the reaction tank 12. FIG. In addition to the raw water tank 10, a mixing tank for adding and mixing ethylenediamine disuccinic acid may be provided on the upstream side of the raw water tank 10 or between the raw water tank 10 and the reaction tank 12.

  When the raw water to be treated contains ethylenediamine disuccinic acid, the step of adding ethylenediamine disuccinic acid may be omitted.

  The ethylenediamine disuccinic acid content is preferably a concentration in the range of 1 mg / L to 3,000 mg / L with respect to the raw water to be treated, and a concentration in the range of 10 mg / L to 1,500 mg / L. More preferably. If the content of ethylenediamine disuccinic acid is less than 1 mg / L, the water content of the generated sludge may be low with little coagulation effect, and if it exceeds 3,000 mg / L, the amount of generated sludge increases and is separated. Separation in the process may be difficult.

  Next, an aggregation treatment is performed on the ethylenediamine disuccinic acid-containing raw water (aggregation treatment step). In the agglomeration treatment, the agglomeration reaction was performed in the reaction step in the reaction vessel 12 by adding the aggregating agent to the ethylenediamine disuccinic acid-containing raw water to be treated and performing agglomeration reaction to obtain an agglomerate. A floc forming step of forming flocs from the agglomerates of the reaction solution, and a floc separation step of separating into flocs and separation liquid by agglomeration precipitation in the agglomeration sedimentation tank 16. Note that a solid-liquid separation process such as a pressure levitation process may be performed instead of the coagulation sedimentation process.

  In the reaction tank 12, the flocculant is added by a pump or the like while being rapidly stirred by a stirring means such as a stirring blade, and agglomeration reaction is performed (reaction step). Thereafter, the reaction solution subjected to the aggregation reaction is sent to the aggregation tank 14.

  The raw water to be treated is not limited as long as it contains a surfactant, particularly an anionic surfactant, but the COD of the raw water is, for example, in the range of 1 mg / L to 50,000 mg / L.

  As the flocculant used in this reaction step, a general inorganic flocculant or the like may be used. As the inorganic flocculant, for example, aluminum sulfate, ferric chloride, polyaluminum chloride, polysilica iron flocculant, etc., or a combination thereof is used, because it is inexpensive, has good cohesiveness, etc. It is preferred to use ferric chloride. Further, as the flocculant, two or more flocculants selected from the above-mentioned inorganic flocculants and organic flocculants described later may be used in combination.

  The addition amount of the inorganic flocculant is preferably a concentration in the range of 500 mg / L or more and 5,000 mg / L or less with respect to the raw water containing ethylenediamine disuccinic acid to be treated, and 1,000 mg / L or more and 3,000 mg / L. A concentration in the range of L or less is more preferable. If the amount added is less than 500 mg / L, the moisture content of the generated sludge may be low, and if it exceeds 5,000 mg / L, the amount of generated sludge increases and separation in the next step may occur. It can be difficult.

  In this reaction process, acid (hydrochloric acid, sulfuric acid or the like) or alkali (sodium hydroxide aqueous solution or the like) may be added to the reaction tank 12 to adjust the pH.

  The pH of the reaction solution during the aggregation reaction is preferably in the range of pH 5 to 6 and more preferably in the range of pH 5.6 to 6.0 from the viewpoint of the aggregation effect. If the pH is higher than 6, the aggregation reaction may not be sufficient and the coloring components may not be removed, and a large amount of aggregating agent may be required to remove the coloring components. On the other hand, if the pH is lower than 5, the solubility of the hydroxide produced from the inorganic flocculant may increase, and the color derived from the flocculant may remain. In particular, ferric chloride is used as an aggregating agent, and an excellent aggregating effect is exhibited by adjusting the pH in the reaction vessel 12 to a range of 5.6 to 6.0.

  In the reaction step, pH adjustment and agglomeration reaction are performed by rapid stirring by a stirring means such as a stirring blade. The stirring speed is preferably in the range of 100 rpm to 500 rpm, and in the range of 250 rpm to 400 rpm. Is more preferable. If the stirring speed is less than 100 rpm, the agglomeration reaction may not be sufficiently performed and fine particles may not be reduced. If the stirring speed is greater than 500 rpm, the aggregate once formed may become fine again.

  In the reaction step, the ethylenediamine disuccinic acid-containing raw water is usually continuously flowed into the reaction tank 12 and the reaction liquid is continuously discharged into the aggregation tank 14. At this time, the residence time in the reaction vessel 12 is preferably in the range of 5 minutes to 20 minutes, and more preferably in the range of 10 minutes to 15 minutes. If the residence time is less than 5 minutes, the reaction may not be sufficient and coloring may not be removed. If it is more than 20 minutes, the processing efficiency may be reduced.

  Next, in the agglomeration tank 14, the reaction liquid transferred from the reaction tank 12 is slowly stirred by stirring means such as a stirring blade to form a floc in which suspended substances in water have grown (floc). Forming step). At this time, an organic flocculant such as a polymer flocculant may be added. This floc mainly contains pigments, release agents, toner particles and the like used in toner production. The floc grows with slow agitation. The solid content concentration of the floc suspension (treatment liquid) obtained at this time is about 0.5 wt% to 1.5 wt%. In addition, the reaction process and the flock formation process may be performed in one tank using the tank in which the reaction tank 12 and the aggregation tank 14 are integrated.

  Examples of organic flocculants include anionic polymer flocculants such as polyacrylamide and sodium polyacrylate; polyacrylamide, polyacrylate, polymethacrylate, polyamine, polydicyandiamide, etc. Cationic polymer flocculants; Nonionic polymer flocculants such as polyacrylamide and polyethylene oxide; Amphoteric polymer flocculants such as dimethylaminoethyl acrylate may be used. It is more preferable to use a polyacrylamide anionic polymer flocculant because of its good aggregation properties. An organic flocculant may be added in the reaction step.

  The amount of the polymer flocculant added is preferably a concentration in the range of 1 mg / L to 50 mg / L with respect to the ethylenediamine disuccinic acid-containing raw water to be treated, preferably in the range of 2 mg / L to 20 mg / L. More preferably, the concentration. If the amount added is less than 1 mg / L, coloring components may remain in the treated water, or the coagulation effect may be small, and the moisture content of the generated sludge may be high. The stickiness of sludge increases and the processability in the next process may deteriorate.

  When flocs grow sufficiently without using a polymer flocculant, a polymer flocculant is not always necessary, but the combination use of an inorganic flocculant and a polymer flocculant is a toner for developing an electrostatic image. For the treatment of raw water containing surfactants, colorants, mold release agents, silica, and other multi-components generated from manufacturing processes using chemical toner manufacturing methods such as emulsion polymerization, suspension polymerization, and dissolution suspension It is effective against this. It is preferable to use ferric chloride as an inorganic flocculant and to use a polyacrylamide anionic polymer flocculant as an organic flocculant in order to grow flocs.

  The floc is grown by stirring with a stirring means such as a stirring blade in the floc forming step. The stirring speed is preferably in the range of 60 rpm to 500 rpm, more preferably in the range of 100 rpm to 300 rpm. When the stirring speed is less than 60 rpm, flocs are not sufficiently formed and fine particles may not be reduced. When the stirring speed is greater than 500 rpm, flocs once formed may become fine again.

  The processing liquid that has floc formed in the coagulation tank 14 is then sent to the coagulation sedimentation tank 16. In the floc forming step, the reaction liquid is normally continuously flowed into the agglomeration tank 14, and the floc-formed treatment liquid is continuously fed to the agglomeration sedimentation tank 16. At this time, the residence time in the coagulation tank 14 is preferably in the range of 5 minutes to 20 minutes, and more preferably in the range of 10 minutes to 15 minutes. If the residence time is less than 5 minutes, flocs are not sufficiently formed, and fine particles may not be reduced. If the residence time is more than 20 minutes, the processing efficiency may be reduced. Further, the water coagulation treatment may be performed in a batch manner in the coagulation tank 14. In this case, the treatment time is preferably in the range of 5 minutes to 15 minutes, and more preferably in the range of 5 minutes to 10 minutes.

  The temperature of water to be treated in the coagulation step is usually in the range of 10 ° C. to 30 ° C., and preferably in the range of 15 ° C. to 25 ° C.

  The processing liquid sent to the coagulation sedimentation tank 16 is separated into a sediment (sludge slurry) in which flocs are concentrated and a separation liquid by natural sedimentation separation in the coagulation sedimentation tank 16 (floc separation step). In the floc separation step, a pressure levitation process or the like may be performed instead of the coagulation sedimentation process, but it is preferable to perform at least one of the coagulation sedimentation process and the pressure levitation process in terms of the amount of sludge generated. . The pressurized levitation treatment is a water treatment method that utilizes the property that air dissolved in a pressurized state is released as fine bubbles when the pressurized water is depressurized. Pressurized water is injected into the pressurized levitation tank. This is a treatment method in which floating substances in water are attached to the generated fine bubbles and floated and separated.

  The separated liquid separated from the sludge slurry in the coagulation sedimentation tank 16 is sent to the biological treatment tank 18 for biological treatment, and dissolved organic matter is removed. In the biological treatment tank 18, dissolved organic substances are decomposed by bacteria or the like that live in the activated sludge, and then separated into activated sludge and supernatant water by natural sedimentation in the subsequent settling tank 20. The supernatant water obtained in the post-precipitation tank 20 is subjected to adsorption treatment of dissolved chemical substances and dissolved organic substances that could not be treated in the biological treatment process by the activated carbon filtration adsorption device 24 after the residual solids are removed by the sand filtration device 22. Then, it is reused or released into rivers. The biological treatment process may be omitted depending on the aqueous state.

  On the other hand, the sludge slurry separated from the separation liquid in the coagulation sedimentation tank 16 and the sludge slurry obtained in the post-precipitation tank 20 are conveyed to the sludge concentrator 26 by a pump or the like. In the sludge concentrator 26, the sludge slurry is separated into a sludge separation liquid which is moisture and a solid content (separation step). In the sludge concentrator 26, for example, it is concentrated by natural sedimentation over about 6 hours to 12 hours. The solid content concentration of the sludge slurry before concentration is about 0.5 wt% or more and 1.5 wt% or less. Moreover, the solid content concentration after concentration is about 2.0 wt% or more and 4.0 wt% or less. When the natural sedimentation in the sludge concentrator 26 is insufficient, the same polymer flocculant as in the floc forming step may be added.

  The sludge slurry after the concentration is dehydrated by the dehydrator 28 (dehydration process) and then processed as industrial waste sludge. In addition, the solid content concentration of the sludge cake after dehydration is about 15 wt% or more and 50 wt% or less. The filtrate generated in the sludge concentrator 26 and the dehydrator 28 is transferred to the raw water tank 10 for storing raw water generated in the toner manufacturing process, mixed with new raw water, and then processed by the above-described water treatment method. May be.

  Examples of the dehydrator 28 include a pressure filter such as a pressure leaf filter, a pressure nutsche, and a filter press, a vacuum filter, and the like, and a filter press is usually used. In addition, centrifugal separation is performed before the dehydration process in terms of reduction in the amount of sludge generated, reduction in processing time, reduction in the amount of coagulant used in the coagulation process, and maintainability of the apparatus. You may dehydrate by centrifugation concentration using an apparatus.

  In the floc separation step of the water treatment method of this embodiment, it is preferable to perform a centrifugal separation process instead of natural sedimentation from the viewpoint of treatment efficiency. The solid-liquid separation time is significantly shortened by the centrifugation process.

  FIG. 2 shows a schematic configuration of an example of a water treatment apparatus provided with a centrifugal separator. In this case, as shown in FIG. 2, the outlet of the coagulation tank 14 is connected to the inlet of the centrifugal separator 30 which is a centrifugal separator by piping or the like, and the outlet of the centrifugal separator 30 and the inlet of the biological treatment tank 18 are connected. Connected by piping. In addition, the inlet of the sludge concentrator 26 is connected to the lower part of the centrifugal separator 30 and the lower part of the post-precipitation tank 20 via piping and the like. The treatment liquid discharged from the aggregating tank 14 is sent to the centrifugal separator 30 by a pump or the like, and is separated into the separation liquid and the sludge slurry in the centrifugal separator 30 (floc separation step).

  The separated liquid and sludge slurry separated from the sludge slurry in the centrifugal separator 30 are treated in the same manner as the water treatment method of FIG. Depending on the properties of the sludge slurry, the treatment by the sludge concentrator 26 may be omitted.

  FIG. 3 is a cross-sectional view of a continuous screw decanter that is an example of the centrifugal separator 30 used in the present embodiment. The screw decanter has an outer body bowl 52 and an inner body screw 54 at the center of the casing 50, and both ends thereof are supported by a shaft seal device and fixed horizontally. The outer body bowl 52 is a bowl in which a cylindrical shape and a conical shape are integrated. The inner cylinder screw 54 includes a pipe 56 and a screw blade 58 welded thereto. The processing liquid discharged from the coagulation tank 14 is supplied into the pipe 56 of the inner cylinder screw 54 through the feed pipe 60, and into the outer cylinder bowl 52 through a plurality of suction liquid discharge ports 62 in the pipe 56. Supplied.

  When the outer bowl 52 is rotated at a high speed, centrifugal separation (for example, a centrifugal effect of about 2,000 G to about 3,500 G, where G is gravitational acceleration) promotes centrifugal separation of solids, and the inner wall of the outer bowl bowl 52 A floc deposit (sludge), which is a solid, is deposited on the surface. At this time, if the inner drum screw 54 is rotated in the same direction as the outer drum bowl 52 while giving a slight rotational difference to the outer drum bowl 52, the sludge concentrate deposited on the inner wall of the outer drum bowl 52 is screw blade 58. Is conveyed to the conical side of the outer shell bowl 52, and is automatically discharged to the outside from the solid discharge port 64 on the inclined surface of the outer shell bowl 52. The solid concentration of the sludge concentrate obtained at this time is about 10% by weight to 20% by weight. Further, the separated liquid after centrifugation is automatically discharged to the outside from the separated liquid discharge port 66 on the large diameter side of the outer shell bowl 52.

  In the water treatment method and the water treatment apparatus according to the embodiment of the present invention, it is preferable that water discharged from the manufacturing process of the electrostatic charge image developing toner using the surfactant be a treatment target. In addition, the water treatment apparatus and the water treatment method according to the present embodiment are manufactured by various chemical toner production methods such as an emulsion polymerization method, a suspension polymerization method, and a dissolution suspension method, in particular, a large amount of a surfactant is used. It is preferably applicable to the treatment of water discharged from the toner production process by the emulsion polymerization method. In the emulsion polymerization method, a resin dispersion formed by emulsion polymerization of a binder resin polymerizable monomer, a colorant, a release agent, and, if necessary, a charge control agent are stirred and mixed in an aqueous solvent. The toner particles are colored resin particles having a predetermined particle size, particle size, shape, and structure by agglomeration and heat fusion. The emulsion polymerization method is roughly divided into a production process of a latex polymer that is a raw material of toner, a production process of a dispersion such as a colorant dispersion and a release agent dispersion, and a production process of a developing toner. Below, an example is given and demonstrated about each.

<Process for producing toner for developing electrostatic image>
(Production process of resin particles)
In order to produce resin particles, a polymerizable monomer and a surfactant are usually added to water and stirred to form an emulsion. Once a polymerizable monomer emulsion is formed, preferably 25 wt% or less of the emulsion (ie, a small amount of emulsion) and a free radical initiator are added to the aqueous phase and mixed and seeded at the desired reaction temperature. To start. After the seed particles are generated, the remaining emulsion is further added to the seed particle-containing composition, and polymerization is continued at a predetermined temperature for a predetermined time to complete the polymerization, thereby generating resin particles (emulsion dispersion). From the production process of this resin particle, it becomes unnecessary in the production process, or is generated by equipment maintenance of the production process, etc., emulsion dispersion containing surfactant, solid particles such as resin particles, surfactant aqueous solution, etc. Is discharged. When the resin particles are generated, they are aggregated together with a colorant dispersion, a release agent dispersion and the like to form aggregated particles, which are then fused to form toner particles.

  The type of the polymerizable monomer is not particularly limited as long as it can react with a free radical initiator. Specific examples of the polymerizable monomer include styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, Esters having a vinyl group such as 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; vinyl nitriles such as acrylonitrile and methacrylonitrile These polymerizable monomers are polymerized to form a homopolymer or a copolymer. Among these, as a resin, at least as a polymerizable monomer, the hydrophilicity is low and a surfactant is attached to the resin surface, and ethylenediamine disuccinic acid easily forms a colloid complex with the surfactant. It is preferable to use a copolymer containing styrene and an ester having a vinyl group, using styrene and an ester having a vinyl group.

  Further, resins such as polyesters and polyurethanes having self-emulsifying properties may be sheared and dispersed in an aqueous medium together with a surfactant. Moreover, what contains an ammonia component as a resin particle is also used.

  As the surfactant used for the production of the resin particles, an anionic surfactant, a cationic surfactant or a nonionic surfactant may be used. Generally, an anionic surfactant is dispersed. It is preferably used because of its strong force and excellent dispersion of resin particles. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of anionic surfactants include fatty acid soaps such as potassium laurate, sodium oleate, and castor oil sodium; sulfate esters such as octyl sulfate, lauryl sulfate, lauryl ether sulfate, and nonyl phenyl ether sulfate; lauryl sulfonate , Sodium alkylarylsulfonates such as dodecylbenzenesulfonate, triisopropylnaphthalenesulfonate, dibutylnaphthalenesulfonate; sulfones such as naphthalenesulfonate formalin condensate, monooctylsulfosuccinate, dioctylsulfosuccinate, lauric acid amide sulfonate, oleic acid amide sulfonate Acid salts; lauryl phosphate, isopropyl phosphate, nonylphenyl ether phosphate Phosphoric acid esters such as Feto; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate; sulfosuccinate salts such as sulfosuccinate lauryl disodium; and the like.

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyldimethylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleylbispolyoxyethylenemethylammonium chloride, lauroylaminopropyldimethylethylammonium ethosulphate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzene Trimethylammonium chloride, Quaternary ammonium salts such as quilts trimethyl ammonium chloride; and the like.

  Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxy Alkyl phenyl ethers such as ethylene nonyl phenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene Alkylamines such as oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkyl amides such as ethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid Alkanolamides such as diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate And so on.

  There is no restriction | limiting in particular as a free radical initiator. Specifically, hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide Ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, tert-butyl hydroperoxide pertriphenyl acetate, tert-butyl formate, Peroxides such as tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, tert-butyl perN- (3-toluyl) carbamate; 2,2 '-Azobispro 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo (methylethyl) diacetate, 2,2'-azobis (2-diaminopropane) hydrochloride, 2,2 ' -Azobis (2-diaminopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2- Methyl methylpropionate, 2,2′-dichloro-2,2′-azobisbutane, 2,2′-azobis-2-methylbutyronitrile, dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (1 -Methylbutyronitrile-3-sodium sulfonate), 2- (4-methylphenylazo) -2-methylmalonodinitrile, 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenyl A Zo-2-methylmalonodinitrile, 2- (4-bromophenylazo) -2-allylmalonodinitrile, 2,2'-azobis-2-methylvaleronitrile, 4,4'-azobis-4-cyanoyoshi Dimethyl herbate, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobiscyclohexanenitrile, 2,2′-azobis-2-propylbutyronitrile, 1,1′-azobis-1 -Chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-cycloheptanenitrile, 1,1'-azobis-1-phenylethane, 1,1'-azobiscumene, 4-Nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphe Nylmethane, 1,1′-azobis-1,2-diphenylethane, poly (bisphenol A-4,4′-azobis-4-cyanopentanoate), poly (tetraethylene glycol-2,2′-azobisiso) Azo compounds such as butyrate); 1,4-bis (pentaethylene) -2-tetrazene, 1,4-dimethoxycarbonyl-1,4-diphenyl-2-tetrazene and the like.

  In the present embodiment, the size of the resin particles is about 0.05 μm or more and 1 μm or less in terms of a volume average particle size measured with a laser diffraction particle size distribution measuring apparatus (Microtrack manufactured by Nikkiso Co., Ltd.).

(Manufacturing process of colorant dispersion and release agent dispersion)
The colorant dispersion is obtained by mixing a colorant, a surfactant and the like in an aqueous phase and performing a dispersion treatment. Similarly, the release agent dispersion is obtained by mixing a release agent, a surfactant and the like in an aqueous phase and performing a dispersion treatment. Coloring that contains solids such as surfactants and colorants, which are no longer necessary in the manufacturing process from the manufacturing process of the colorant dispersion and the release agent dispersion, or are generated by equipment maintenance in the manufacturing process. An agent dispersion, a release agent dispersion containing a solid content such as a surfactant and a release agent, an aqueous surfactant solution and the like are discharged.

  Examples of the colorant include carbon black, chrome yellow, hansa yellow, benzidine yellow, selenium yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliant carmine 3B, brilliant carmine 6B, and Dupont. Oil red, pyrazolone red, resol red, rhodamine B rake, lake red C, rose bengal, aniline blue, ultramarine blue, chalcoa oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate, etc. Pigment: Acridine, xanthene, azo, benzoquinone, azine, anthraquinone, dioxadi System, thiazine, azomethine, indigo, thioindigo, phthalocyanine, aniline black, polymethine, triphenylmethane dyes, diphenylmethane dyes, and various dyes such as thiazole system. These colorants may be used alone or in combination of two or more.

  The size of the colorant in the colorant dispersion is, for example, about 0.05 μm or more and 0.5 μm or less in the volume average particle size measured by the laser diffraction particle size distribution measuring apparatus (Microtrack manufactured by Nikkiso Co., Ltd.). It is.

  The type of wax that acts as a mold release agent is not particularly limited. For example, low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene; silicones having a softening point; oleic acid amide, erucic acid amide, ricinoleic acid amide, Fatty acid amides such as stearamide; plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, micro And mineral waxes such as crystallin wax and Fischer-Tropsch wax; and ester waxes of higher fatty acids such as stearyl stearate and behenyl behenate and higher alcohols. The melting point of the release agent is, for example, in the range of 50 ° C. to 100 ° C., and preferably in the range of 70 ° C. to 100 ° C.

  The size of the release agent in the release agent dispersion is, for example, 0.05 μm or more and 0.5 μm in volume average particle diameter measured with the laser diffraction particle size distribution measuring apparatus (Microtrack manufactured by Nikkiso Co., Ltd.). It is about the following.

  Examples of the surfactant include the same surfactants used for the production of the resin particles.

(Toner manufacturing process)
The resin particles obtained by the above preparation method are used for toner preparation by the following method, for example. Resin particle dispersion containing resin particles obtained by the above preparation method, a colorant dispersion, a release agent dispersion, an aggregating agent if necessary, a charge control agent if necessary, and a necessity In response to mixing with other additives, the resulting mixture is effective to form aggregated particles at a temperature around the glass transition temperature (Tg) of the resin particles, preferably at Tg ± 10 ° C. of the resin particles. Heating is performed for a long time, for example, 1 hour to 8 hours to form toner-sized aggregated particles (aggregation step). Next, the pH in the aggregation system is adjusted to stop the aggregation growth of the aggregated particles (stop process). The agglomerated particle suspension is heated to a Tg of the resin particles or higher, preferably Tg + 40 ° C. of the resin particles, for example, about 60 ° C. to about 120 ° C. to coalesce or fuse to form toner particles. (Fusion step) The toner particles are separated from the mother liquor by means such as filtration, washed with ion-exchanged water (washing step), and then dried.

  The resin particles are usually used as a binder resin for the toner, and are present in the toner in an amount of about 75 wt% to 98 wt% with respect to the solid content of the toner.

  The colorant is usually present in the toner in an amount effective for coloring, for example, about 1% by weight to 15% by weight, preferably about 3% by weight to 10% by weight, based on the solid content of the toner.

  A preferable amount of the wax that acts as a release agent is about 5% by weight or more and 20% by weight or less based on the solid content of the toner.

  The coagulant used as necessary may be used in an amount effective for fusion, for example, about 0.01% by weight to 10% by weight with respect to the solid content of the toner. As the aggregating agent to be used, a compound having a monovalent or higher charge is preferable. Specific examples of the compound include the aforementioned anionic surfactants; acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid; Examples include, but are not limited to, salts such as magnesium, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, sodium carbonate, and polyaluminum chloride. Preferred flocculants include those having a nitrogen component such as nitric acid.

  The charge control agent may be used in an amount effective for charging, for example, 0.1 wt% or more and 5 wt% or less with respect to the solid content of the toner. Suitable charge control agents include, but are not limited to, alkyl pyridinium halides, bisulfates, charge control agents such as silica, and negative charge control agents such as aluminum complexes.

  In addition, inorganic particles or the like may be wet-added as an additive as necessary. Examples of inorganic particles to be wet-added include silica, alumina, titania, calcium carbonate, magnesium carbonate, and tricalcium phosphate, all of which are usually used as external additives on the toner surface, such as ionic surfactants and polymers. You may disperse | distribute in water with an acid, a polymer base, etc., and add wet as an inorganic particle dispersion liquid, such as a silica.

  The size of the inorganic particles used in the present embodiment in the dispersion is a volume average particle size measured by the laser diffraction particle size distribution measuring apparatus (Microtrack manufactured by Nikkiso Co., Ltd.) and is about 4 nm to 150 nm.

  The manufacturing process (including the toner cleaning process) such as the resin particle manufacturing process, the colorant dispersion manufacturing process, the release agent dispersion manufacturing process, and the toner manufacturing process is not necessary in the manufacturing process. Or a surfactant aqueous solution containing a solid content such as a surfactant, a colorant, a release agent, inorganic particles, and a toner generated by equipment maintenance in the manufacturing process, an emulsion dispersion, a colorant dispersion, Surfactant-containing liquids such as release agent dispersion liquid, inorganic particle dispersion liquid, toner dispersion liquid, and apparatus cleaning water are discharged. These raw waters are collected in a raw water tank and treated by the above water treatment method.

  The water treatment method according to this embodiment may be applied to the treatment of raw water containing a surfactant discharged from a production process of a toner for developing an electrostatic charge image by a chemical toner production method such as an emulsion polymerization method. Of those steps, among those steps, discharged from the pigment dispersion production step, release agent dispersion production step, toner fusion step, toner washing step, etc., for example, the surfactant content is 0.1 wt% or more It is applied to the treatment of liquids of 4% by weight or less. When the surfactant content is lower than 0.1% by weight, a technique such as membrane separation may be applied. Thus, in consideration of the treatment efficiency of water treatment, different water treatment methods may be applied according to the amount of surfactant contained in the water discharged from each step. In addition, the liquid discharged from the latex polymer (emulsion dispersion) manufacturing process may be difficult to concentrate, such as centrifugal concentration, so other water treatments, such as a heated acid decomposition method using concentrated sulfuric acid. A method may be applied.

  The water treatment method according to the present embodiment may be applied to the treatment of water containing solid content discharged from the production process of a toner for developing an electrostatic charge image by a chemical toner production method such as an emulsion polymerization method as described above. preferable.

  Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely in detail, the present invention is not limited to the following examples.

<Example of production of toner for developing electrostatic image>
In the following, an example of producing an electrostatic charge image developing toner in which water subjected to water treatment in this example and a comparative example is discharged will be shown.

(Preparation of emulsion dispersion (resin particle dispersion))
Styrene 320 parts by weight n-butyl acrylate 80 parts by weight Acrylic acid 10 parts by weight Dodecanethiol 10 parts by weight This solution 420 parts by weight, nonionic surfactant (manufactured by Sanyo Chemical Industries, Nonipol 400) 6 parts by weight, and anionic A solution obtained by dissolving 10 parts by weight of a surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) in 550 parts by weight of ion-exchanged water is placed in a flask to disperse and emulsify, and while stirring and mixing slowly for 10 minutes, 50 parts by weight of ion-exchanged water in which 4 parts by weight of ammonium persulfate was dissolved was added. Thereafter, the inside of the flask was sufficiently replaced with nitrogen and then heated with stirring in an oil bath until the temperature in the system reached 70 ° C., and emulsion polymerization was continued for 5 hours to obtain an emulsion dispersion.

The resin particles obtained from the emulsion dispersion were 155 nm when the volume average particle diameter (D ₅₀ ) of the resin particles was measured with a laser diffraction particle size distribution analyzer (Microtrack manufactured by Nikkiso Co., Ltd.), and a differential scanning calorimeter ( When the glass transition point of the resin was measured at a heating rate of 10 ° C / min using Shimadzu Corporation, DSC-50), it was 54 ° C, and a molecular weight measuring instrument (HLC-8020, manufactured by Tosoh Corporation) was used. It was 33,000 when the weight average molecular weight (polystyrene conversion) was measured using THF as a solvent.

(Preparation of colorant dispersion)
Pigment 150 parts by weight Anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 20 parts by weight Ion-exchanged water 400 parts by weight The above is mixed and dispersed with an optimizer, and a colorant dispersion is obtained. Prepared. The pigment is C.I. for yellow. I. Pigment Yellow 74 (manufactured by Dainichi Seika), C.I. I. Pigment Blue 15: 3 (manufactured by BASF), C.I. I. Pigment Red 122 (manufactured by Dainichi Seika Co., Ltd.) and carbon black (manufactured by Cabot Corp.) were used.

(Preparation of release agent dispersion)
Paraffin wax (manufactured by Nippon Seiwa Co., Ltd., HNP0190, melting point 85 ° C.) 50 parts by weight Cationic surfactant (manufactured by Kao Corporation, Sanizol B50) 5 parts by weight Ion-exchanged water 200 parts by weight Heated to 95 ° C. Then, after dispersing using a homogenizer (IQA Ultra Turrax T50), the dispersion is performed with a pressure discharge type homogenizer, and a release agent having a volume average particle size of 550 nm is dispersed. A liquid was prepared.

(Preparation of aggregated particles)
Emulsion dispersion 200 parts by weight Colorant dispersion 30 parts by weight Release agent dispersion 70 parts by weight Cationic surfactant (manufactured by Kao Corporation, SANISOL B50) 1.5 parts by weight In a round stainless steel flask After mixing and dispersing using a homogenizer (manufactured by IKA, Ultra Tarrax T50), the mixture was heated to 48 ° C. while stirring the inside of the flask in a heating oil bath. After maintaining at 48 ° C. for 30 minutes, observation with an optical microscope confirmed that aggregated particles (volume: 95 cm ³ ) having an average particle diameter of about 5 μm were formed.

(Preparation of adhered particles)
60 parts by weight of the resin particle dispersion was gently added to the prepared dispersion of aggregated particles. The volume of the resin particles contained in the resin particle dispersion was 25 cm ³ . And the temperature of the heating oil bath was raised to 50 degreeC, and was hold | maintained for 1 hour. When observed with an optical microscope, it was confirmed that adhered particles having an average particle diameter of about 5.7 μm were formed.

  Then, after adding 3 parts by weight of an anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) to the prepared dispersion of the adhered particles, the stainless steel flask is sealed and a magnetic seal is used. The mixture was heated to 105 ° C. and kept for 3 hours while stirring was continued. Then, after cooling, the reaction product was filtered, washed thoroughly with ion-exchanged water, and then dried to obtain an electrostatic image developing toner.

(Composition of water 1 to be treated)
The processing target water 1 is water discharged from a manufacturing factory that manufactures the toner for developing an electrostatic charge image, and includes a pigment dispersion, a release agent (wax) dispersion, an emulsion dispersion, Water containing an aqueous surfactant solution and the like. It is presumed that the main composition of the water 1 to be treated is as follows from the materials used for the preparation of the toner. The solid content concentration of this water was 0.01% by weight, and the chemical oxygen demand (COD) was 87 mg / L.
Surfactant 0.008 part by weight Latex polymer 0.070 part by weight Colorant 0.016 part by weight Wax 0.012 part by weight Water 999.9 part by weight Ethylenediamine disuccinic acid (EDDS, manufactured by Crest Co., Ltd.) is added to this water. 0.5 weight part (500 mg / L with respect to the raw | natural water to process) was added, and what was mixed and stirred for 30 minutes was made into the process target water 1. FIG.

  The solid content concentration was measured by a method in which a water sample was placed in an aluminum container and the water was evaporated in an oven. The chemical oxygen demand was measured by a method defined in JIS K 0102 17. Specifically, this is a test method in which an oxidant is added to a sample and allowed to react under a certain condition, and the amount of oxidant consumed at that time is expressed in terms of oxygen.

(Composition of water 2 to be treated)
The treatment target water 2 was the same as the treatment target water 1 except that ethylenediamine disuccinic acid was not added.

(Composition of water 3 to be treated)
Except for the addition amount of ethylenediamine disuccinic acid being 1.5 parts by weight (1,500 mg / L with respect to the raw water to be treated), the concentration and composition are the same as the treatment target water 1 and the treatment target water 3 did.

(Composition of water 4 to be treated)
The treatment target water 4 was the same as the treatment target water 1 except that the amount of ethylenediamine disuccinic acid added was 0.01 parts by weight (10 mg / L with respect to the raw water to be treated).

(Composition of water 5 to be treated)
Except for the addition amount of ethylenediamine disuccinic acid being 3.0 parts by weight (3,000 mg / L with respect to the raw water to be treated), the treatment target water 5 is the same as the treatment target water 1 in concentration and composition. did.

(Composition of water 6 to be treated)
The treatment target water 6 was the same as the treatment target water 1 except that the amount of ethylenediamine disuccinic acid added was 0.001 part by weight (1 mg / L with respect to the raw water to be treated).

Example 1
[Treatment of target water 1]
The water 1 to be treated was treated using the water treatment apparatus shown in FIG. The water 1 to be treated is first stored in the raw water tank 10, and then sent to the reaction tank 12 by a pump, and 1,000 mg / L of an inorganic flocculant (ferric chloride) is added, and the stirring speed is 500 rpm and the residence time. In 10 minutes, the aggregation reaction was performed at pH 5.7. Next, the obtained reaction solution is pumped to a flocculation tank 14 (18 m ³ ), and 1 mg / L of a polymer flocculant (acrylamide polymer flocculant: Hymolock SS-100: manufactured by Hymo Co.) is added. Then, flocs were formed at a stirring speed of 300 rpm and a residence time of 10 minutes. Flock formation was good. Next, the processing liquid floc-formed in the coagulation tank 14 was sent to the coagulation sedimentation tank 16 by a pump. The fed processing liquid was separated into sludge slurry and flocs in which flocs were concentrated by natural sedimentation separation in the coagulation sedimentation tank 16. The time required for the separation was 1 hour. The separated liquid separated from the sludge slurry in the coagulation sedimentation tank 16 is pumped to the biological treatment tank 18 for biological treatment (activated sludge treatment), and then activated sludge and supernatant water by natural sedimentation in the post-precipitation tank 20. The supernatant water was subjected to adsorption treatment of dissolved organic matter with the activated carbon filtration adsorption device 24 after removing the remaining solids with the sand filtration device 22. The chemical oxygen demand of this treated water was <5 mg / L. Further, the sludge slurry separated from the separation liquid in the coagulation sedimentation tank 16 and the sludge slurry obtained in the post-precipitation tank 20 are concentrated by natural sedimentation in the sludge concentrator 26 and dehydrated by the dehydrator 28 (filter press). Through the treatment process, it was recovered as sludge. Although the water 1 to be treated was treated with 18 m ³ , the final sludge generation amount was 1.1 g / L. The results are shown in Table 1.

(Example 2)
[Treatment of target water 1]
The water 1 to be treated was treated using the water treatment apparatus shown in FIG. The water 1 to be treated is first stored in the raw water tank 10, and then sent to the reaction tank 12 by a pump, and 1,000 mg / L of an inorganic flocculant (ferric chloride) is added, and the stirring speed is 500 rpm and the residence time. The aggregation reaction was performed at pH 5.8 in 10 minutes. Next, the obtained reaction liquid is sent to the coagulation tank 14 by a pump, and 1 mg / L of a polymer coagulant (acrylamide polymer coagulant: Hymolock SS-100: manufactured by Hymo Co.) is added, and the stirring speed is increased. Flock formation was performed at 300 rpm and a residence time of 10 minutes. Flock formation was good. Next, the processing liquid floc formed in the aggregation tank 14 was sent to the centrifugal separator 30 by a pump. As the centrifugal separator 30, a screw decanter (HS type manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd., see FIG. 3) having a centrifugal effect of 3,000 G was used and processed in a normal operation (18 m ³ / hr). The time required for the separation was 1 hour. The separated liquid separated from the sludge slurry in the centrifugal separator 30 is sent to the biological treatment tank 18 by a pump for biological treatment (activated sludge treatment), and then activated sludge and supernatant water by natural sedimentation in the post-precipitation tank 20. The supernatant water was subjected to adsorption treatment of dissolved organic matter with the activated carbon filtration adsorption device 24 after removing the remaining solids with the sand filtration device 22. The chemical oxygen demand of this treated water was <5 mg / L. The sludge slurry separated from the separation liquid in the centrifugal separator 30 and the sludge slurry obtained in the post-precipitation tank 20 are concentrated by natural sedimentation in the sludge concentrator 26 and dehydrated by the dehydrator 28 (filter press). Through the treatment process, it was recovered as sludge. Although the water 1 to be treated was treated with 18 m ³ , the final sludge generation amount was 1.0 g / L. The results are shown in Table 1.

(Example 3)
[Treatment of water 3 to be treated]
The process similar to Example 1 was performed except having used the process target water 3. FIG. The results are shown in Table 1.

Example 4
[Treatment of water 4 to be treated]
The process similar to Example 1 was performed except having used the process target water 4. FIG. The results are shown in Table 1.

(Example 5)
[Treatment of water 5 to be treated]
The process similar to Example 1 was performed except having used the process target water 5. FIG. The results are shown in Table 1.

(Example 6)
[Treatment of water 6 to be treated]
The same treatment as in Example 1 was performed except that the treatment target water 6 was used. The results are shown in Table 1.

(Comparative Example 1)
[Treatment of target water 2]
Except for using water 2 to be treated, the same treatment as in Example 1 was performed, but since the agglutination reaction was not good, 1,000 mg / L inorganic flocculant (ferric chloride) was further added, Aggregation is carried out, and then the obtained reaction solution is pumped to the aggregation tank 14 and 2 mg / L of a polymer flocculant (acrylamide polymer flocculant: Hymolock SS-100: manufactured by Hymo Co.) is added. Then, flocs were formed at a stirring speed of 300 rpm and a residence time of 10 minutes. Flock formation was good. Next, the processing liquid floc-formed in the coagulation tank 14 was sent to the coagulation sedimentation tank 16 by a pump. The fed processing liquid was separated into sludge slurry and flocs in which flocs were concentrated by natural sedimentation separation in the coagulation sedimentation tank 16. The time required for the separation was 5 hours. The separated liquid separated from the sludge slurry in the coagulation sedimentation tank 16 is pumped to the biological treatment tank 18 for biological treatment (activated sludge treatment), and then activated sludge and supernatant water by natural sedimentation in the post-precipitation tank 20. The supernatant water was subjected to adsorption treatment of dissolved organic matter with the activated carbon filtration adsorption device 24 after removing the remaining solids with the sand filtration device 22. The chemical oxygen demand of this treated water was <5 mg / L. Further, the sludge slurry separated from the separation liquid in the coagulation sedimentation tank 16 and the sludge slurry obtained in the post-precipitation tank 20 are concentrated by natural sedimentation in the sludge concentrator 26 and dehydrated by the dehydrator 28 (filter press). Through the treatment process, it was recovered as sludge. Although the water 2 to be treated was treated with 18 m ³ , the final sludge generation amount was 10 g / L. The results are shown in Table 1.

(Comparative Example 2)
[Treatment of target water 2]
Except for using the water 2 to be treated, the same treatment as in Example 2 was performed, but the aggregation reaction was not good, so an additional 1,000 mg / L inorganic flocculant (ferric chloride) was added, Aggregation is carried out, and then the obtained reaction solution is pumped to the aggregation tank 14 and 2 mg / L of a polymer flocculant (acrylamide polymer flocculant: Hymolock SS-100: manufactured by Hymo Co.) is added. Then, flocs were formed at a stirring speed of 300 rpm and a residence time of 10 minutes. Flock formation was good. Next, the treatment liquid floc-formed in the aggregation tank 14 was sent to the centrifugal separator 30 by a pump and processed in a normal operation (18 m ³ / hr). The time required for the separation was 3 hours. The separated liquid separated from the sludge slurry in the centrifugal separator 30 is sent to the biological treatment tank 18 by a pump for biological treatment (activated sludge treatment), and then activated sludge and supernatant water by natural sedimentation in the post-precipitation tank 20. The supernatant water was subjected to adsorption treatment of dissolved organic matter with the activated carbon filtration adsorption device 24 after removing the remaining solids with the sand filtration device 22. The chemical oxygen demand of this treated water was <5 mg / L. The sludge slurry separated from the separation liquid in the centrifugal separator 30 and the sludge slurry obtained in the post-precipitation tank 20 are concentrated by natural sedimentation in the sludge concentrator 26 and dehydrated by the dehydrator 28 (filter press). Through the treatment process, it was recovered as sludge. Although the water 1 to be treated was treated with 18 m ³ , the final sludge generation amount was 8 g / L. The results are shown in Table 1.

  As shown in Table 1, in Examples 1 to 6 using treatment water 1, 3 to 6 to which ethylenediamine disuccinic acid was added, Comparative Example 1 using treatment water 2 to which ethylenediamine disuccinic acid was not added Compared to 2, the treatment was more efficient, and the amount of flocculant used and the amount of sludge generated were reduced.

It is a schematic structure figure showing an example of the water treatment equipment concerning the embodiment of the present invention. It is a schematic block diagram which shows the other example of the water treatment apparatus which concerns on embodiment of this invention. It is a schematic block diagram which shows an example of the centrifuge used for the water treatment method which concerns on embodiment of this invention.

Explanation of symbols

  1, 3 Water treatment equipment, 10 Raw water tank, 12 Reaction tank, 14 Coagulation tank, 16 Coagulation sedimentation tank, 18 Biological treatment tank, 20 Post sedimentation tank, 22 Sand filtration apparatus, 24 Activated carbon filtration adsorption apparatus, 26 Sludge concentration apparatus, 28 Dehydrator, 30 Centrifugal separator, 50 Casing, 52 Outer shell bowl, 54 Inner shell screw, 56 Pipe, 58 Screw blade, 60 Feed pipe, 62 Suction liquid discharge port, 64 Solid matter discharge port, 66 Separation liquid discharge port .

Claims (1)

A resin particle dispersion in which resin particles are dispersed, a colorant dispersion in which a colorant is dispersed, and a release agent dispersion in which a release agent is dispersed to form an aggregate particle,
A stopping step of adjusting the pH in the aggregation system to stop the aggregation growth of the aggregated particles;
A fusion step in which the agglomerated particles are heated to a temperature equal to or higher than the glass transition temperature of the resin particles to fuse them;
The raw water containing a surfactant generated from the manufacturing process of the electrostatic charge image developing toner containing
An ethylenediamine disuccinic acid addition step of adding ethylenediamine disuccinic acid to the raw water,
A reaction step in which a flocculant is added to raw water containing ethylenediamine disuccinic acid and agglomeration reaction is performed;
A floc forming step of forming a floc from the aggregate that has undergone agglomeration reaction in the reaction step;
A floc separation step for separating the floc into a separation liquid;
Water treatment method, which comprises a.

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