TWI746638B - Method for producing water-purifying agent and method for treating wastewater - Google Patents

Abstract

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Description

Water purification agent manufacturing method and discharged water treatment method

The present invention relates to a method for manufacturing a plant-derived water purification agent used for water purification of industrial discharge water and the like, and a discharge water treatment method using the water purification agent.

In recent years, in the process of manufacturing various products in factories, a large number of waste liquids containing environmentally hazardous substances such as metal ions or fluoride ions have been generated. On the other hand, the emission regulations for these inorganic ions have gradually become stricter. In order to comply with these emission regulations, the present inventors seek a method for removing inorganic ions that can efficiently remove inorganic ions from the discharged water containing inorganic ions and implement it in a simple and low-cost manner as much as possible. As far as methods for removing impurity particles such as water discharged from factories are concerned, some people have proposed agglomeration precipitation method, ion exchange method, adsorption method using adsorbents such as activated carbon, electrosorption method, and magnetic adsorption method.

For example, with regard to the agglomeration precipitation method, a method has been proposed, which includes: adding alkali to the discharged water in which heavy metal ions are dissolved, and making the discharged water alkaline, and then insolubilizing at least a part of the heavy metal ions , And then the step of forming a suspended solid; adding an inorganic flocculant to the discharged water to make the suspended solid coagulate and settle; and let the discharged water pass through leafy vegetables such as jute (mulukhiya) and komatsuna (komatsuna) The adsorption step of the adsorption layer of the cation exchanger (for example, refer to Patent Document 1). At the same time, some people have also proposed an agglutination method, which is to mix or use a polymer flocculant with a flocculant containing at least any one of jute cabbage, its dried product, or its extract, and then aggregate the fine particles in the suspension. Separation (for example, refer to Patent Document 2).

In addition, when the amount of discharged water to be purified increases, the amount of unnecessary substances contained in the discharged water increases, or the types of unnecessary substances contained in the discharged water increase, it is desirable to construct a type of discharged water. A system that automatically puts the necessary purifying agent in the purification process. In addition to performing high-speed and stable purification processing, the automation of the device is an important issue, and in addition to providing an automatic purification device exhibiting stable purification performance, it is also desired to provide a water purifier suitable for the automatic purification device. However, the methods described in Patent Document 1 and Patent Document 2 are completely unaware of automated devices for purifying wastewater, and the water purifiers described in these documents are not suitable for supplying to automated system devices. Therefore, a water purifying agent made of particles containing a mixture of plant powder and a polymer flocculant has been proposed as a water purifying agent that can be suitably used in an automated purification device (for example, refer to Patent Document 3).

[Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Application Publication No. 2011-194385 [Patent Document 2] Japanese Patent Application Publication No. 11-114313 [Patent Document 3] Japanese Patent Application Publication No. 2016-73898

[Problem to be solved by the invention] However, when the automatic purification device is enlarged, especially when the size of the drain tank is used for supplying to a large automatic purification device, it is low-cost and stable without changing every time. As far as purification performance is concerned, we understand that the water purification agent described in Patent Document 3 is insufficient. Therefore, the present inventors desire to provide a water purifier, which can also be applied to a water purifier when the size of a drain tank is used in a large automatic purification device, and which is low-cost and stable with no change every time. Purification performance.

The present invention solves multiple problems in the past, and aims to achieve the following objects as a subject. That is, the object of the present invention is to provide a water purifier, which can also be applied to the water purifier when the size of the discharge water tank is used in a large automatic purification device, and it is low-cost and can display unchanged every time The stable purification performance.

[Means for Solving the Problem] The means for solving the problem are as follows. That is: <1> A method for manufacturing a water purifying agent, which is a method for manufacturing a water purifying agent made of particles containing plant powder and a polymer flocculant, which includes: a kneading step, mixing plant powder with high Molecular coagulant kneading; wherein, in the aforementioned kneading step, the hardness of the kneaded product obtained through the aforementioned kneading step is kneaded so that the stress is 3N/mm ² ~ 100N/mm ^{2 under the following measurement conditions} Plant powder and polymer agglutinant; Measurement conditions: For the aforementioned kneaded material, use a stress-controlled rheometer (viscosity measuring device) to measure when a probe with a diameter of 16mm is pushed in at a speed of 30mm/min, and the amount is pushed into Stress at 5mm. <2> The method for producing a water purifying agent as described in the above <1>, which meets any one of the following (a1), the following (a2), and the following (b): (a1): First In the kneading step, water is mixed with the polymer flocculant to knead the polymer flocculant and water; after that, the second kneading step is performed to mix the plant powder with the kneaded polymer flocculant to knead the plant Powder and polymer flocculant; wherein, in the first kneading step, the total amount (mass) of water mixing relative to the solid content (mass) in the water purifying agent is 1.5 to 8 times; (a2): In the first kneading step, water is mixed with the polymer flocculant to knead the polymer flocculant and water; after that, the second kneading step is performed to mix the plant powder and water to the kneaded polymer flocculant, The plant powder and the polymer flocculant are kneaded; wherein, in the first kneading step and the second kneading step, the total amount (mass) of the water mixed with respect to the solid content (mass) in the water purifying agent is 1.5 times to 8 times; and (b): mixing step, mixing plant powder with polymer flocculant and water to knead them; wherein, in the aforementioned mixing step, relative to the solid content (mass ), the total amount (mass) of water mixing is 1.5 to 8 times. <3> The method for producing a water purifier as described in the above <1>, which includes: a first kneading step, mixing water with the polymer flocculant to knead the polymer flocculant and water; In the second kneading step, the plant powder is mixed with the kneaded polymer flocculant to knead the plant powder and the polymer flocculant. <4> The method for producing a water purifier as described in any one of the above <1> to <3>, wherein the total value of the kneading time at the time of kneading is 15 minutes or more under the condition of a rotation speed of 80 rpm to 150 rpm And within 30 minutes. <5> The method for producing a water purifying agent as described in any one of the aforementioned <1> to <4>, wherein the plant powder is selected from changshuohuangma, jute, small pine cabbage, and celery , Japanese turnip and any one of the group consisting of Bocai. <6> The method for producing a water purifying agent as described in the above <5>, wherein the plant powder is Changshuo jute. <7> The manufacturing method of the water purifier as described in the above <6>, wherein the Changshuo jute is "Zhonghuang Ma No. 4" under the identification number 2013 of the Bast Fiber Research Institute of the Chinese Academy of Agricultural Sciences. <8> The method for producing a water purifying agent according to any one of the aforementioned <1> to <7>, wherein the median diameter of the water purifying agent is 150 μm or more. <9> The method for producing a water purifying agent according to any one of the aforementioned <1> to <8>, wherein the polymer flocculant is polyacrylamide. <10> The method for producing a water purifying agent as described in any one of the aforementioned <1> to <9>, which comprises: a forming step, forming a molded body with a kneaded product obtained through the aforementioned kneading step; drying Step, drying the aforementioned shaped body; and pulverizing step, pulverizing the dried shaped body. <11> A discharge water treatment method, which is to dissolve the water purifier obtained by the method of manufacturing the water purifier described in any one of the above <1> to <10> in water to obtain a plant powder and high The dispersion liquid of the molecular coagulant is then supplied to the discharged water containing the inorganic waste to remove the inorganic waste in the discharged water. <12> The discharged water treatment method as described in the aforementioned <11>, wherein the discharged water system has at least one selected from the group consisting of nickel, fluorine, iron, copper, zinc, chromium, arsenic, cadmium, and lead Inorganic waste. <13> The discharge water treatment method described in the above <11> or <12>, wherein the conductivity of the water in the dispersion is 30 μS/cm or more.

[Effects of the Invention] According to the present invention, it is possible to solve multiple problems in the past and achieve the aforementioned objects, and to provide a water purifier, which can also be applied to the size of a discharge tank for use in a large automated purification device The water purifier is low-cost and can show stable purification performance that does not change every time.

(Manufacturing method of water purifying agent) The water purifying agent manufactured by the manufacturing method of the water purifying agent of the present invention (hereinafter also referred to as the manufacturing method of the present invention) is made of particles containing plant powder and a polymer coagulant. The manufacturing method of the present invention includes a kneading step of kneading a plant powder and a polymer flocculant, and, if necessary, includes other steps such as a forming step, a drying step, and a crushing step. The manufacturing method of the present invention is characterized in that, in the aforementioned kneading step, the hardness of the kneaded product obtained through the aforementioned kneading step is such that the stress is 3N/mm ² to 100 N/mm ^{2 under the following measurement conditions.} , To mix plant powder and polymer flocculant. Measurement conditions: For the aforementioned mixture, use a stress-controlled rheometer (viscosity measuring device) to measure the stress when a probe with a diameter of 16 mm is pushed in at a speed of 30 mm/min, and the amount of pressure is 5 mm.

After obtaining the above-mentioned kneaded product with the desired hardness, the following manufacturing method is more preferable. The production method of the present invention defines the total amount (mass) of water mixing when kneading the polymer flocculant and water, or when kneading the plant powder and the polymer flocculant. The total amount (mass) of the water mixing relative to the solid content (mass) in the aforementioned water purification agent is 1.5 to 8 times. In addition, the production method of the present invention defines a kneading step of mixing water with a polymer flocculant and kneading the polymer flocculant and water before the kneading step of kneading the plant powder and the polymer flocculant. The water purifier system manufactured by the manufacturing method of the present invention that satisfies the above requirements can be applied to the water purifier when the size of the drain tank is used in a large automatic purification device, and it is low-cost and can display unchanged every time Water purifier with stable purification performance.

When the water purifier is used to purify the discharged water, the method of adding the water purifier can include the method of directly adding the discharged water to the water purifier, and the method of first dissolving the water purifier in water to obtain plant powder and A method of dispersing the polymer flocculant into the drain water, etc. However, if the automatic purification device is enlarged, especially when the size of the drain tank becomes larger, in the case of a granular water purifier, it will form a stable and uniform dispersion state every time and maintain constant water purification performance. , This system becomes difficult. Therefore, in an automated purification device in which the size of the drain water tank is large, it becomes necessary to use a purification method of the drain water using a dispersion liquid. Therefore, the inventors of the present invention conducted repeated studies on the purification treatment of the discharged water using the dispersion, and found that the viscosity of the dispersion changes when the plant powder and the polymer flocculant are dissolved according to the type of water in the dispersion. Next, the inventors obtained the following insights: the difference in the viscosity of the dispersion liquid will affect the purification performance of the discharged water, and in order to obtain good purification performance, it is effective to increase the viscosity of the dispersion liquid to some extent. Specifically, although tap water and underground water systems are typically cheaper, when using water with high conductivity due to the influence of ions contained in it to obtain a dispersion, if the dispersion is added to the drain water , The viscosity of the discharged water decreases, and solid components such as plant powders settle in a short time. As a result, sufficient inorganic ion adsorption performance cannot be obtained. On the other hand, as an alternative to tap water and groundwater, if distilled water with low conductivity is used, such problems will not occur. However, distilled water is expensive, and its cost becomes a huge burden in semiconductor factories and electroplating factories that process a large amount of discharged water every day. Therefore, when the present inventors conducted further research, they found a water purifier that can reduce the concentration of inorganic ions in the discharged water to a desired level even if it uses tap water and groundwater, which are typically relatively inexpensive, as a dispersion. The concentration is lower than the concentration.

The present inventors realized that even the dispersion of tap water and groundwater can increase its viscosity. This is due to the adjustment of kneaded plant powder and polymer flocculant in the production method of the water purifier. The hardness of the obtained mixture is effective. Here, the hardness of the kneaded product can be obtained using the AR-G2 hardness measurement mode manufactured by TA Instruments, which is a stress control type rheometer (viscosity measuring device). Specifically, approximately 7.5 g of the kneaded material is filled in a polypropylene cylindrical container with an inner diameter of 22 mm in diameter and 11 mm in depth, and a probe with a diameter of 16 mm is used to measure when it is pushed at a pushing speed of 30 mm/min. The stress when the pushing amount is 5mm. In the present invention, the stress measured under this condition is called "hardness". As a result, the hardness of the kneaded product is preferably in the range of 3N/mm ² to 100 N/mm ² . Next, the present inventors discovered that in order to obtain the desired hardness of the kneaded product, it is important to perform the steps shown in (i) or (ii) below. (I) In the method of manufacturing a water purifier, when a polymer flocculant and water are kneaded, or when a plant powder and a polymer flocculant are kneaded, relative to the solid content (mass) in the water purifier, the water is mixed The total amount (quality) is 1.5 times to 8 times. (Ii) In the method of manufacturing the water purifier, before the kneading step of kneading the plant powder and the polymer flocculant, a kneading step of mixing water with the polymer flocculant and kneading the polymer flocculant and water is performed.

In this way, if a step of adding a large amount of water to the polymer flocculant and kneading is performed, or a step of kneading the polymer flocculant and water in advance is performed before kneading with the plant powder, a kneaded product with the desired hardness can be formed. In addition, the water purifier produced by such a mixture can increase the viscosity of the dispersion in which the water purifier is dispersed, and increase the viscosity of the discharged water after the dispersion is injected. Although the reason is not clear, it can be considered as follows: Under these conditions, whether the agglutination of the molecular chains of the polymer flocculant is solved to some extent by kneading and the improvement of its solubility with water is done. Make effective contributions.

Hereinafter, the specific structure of the water purifying agent manufacturing method is divided into (A) the first aspect and (B) the second aspect, and the detailed description will be given.

<A; The first aspect of the method of producing a water purifier> In the method of producing the water purifier, when the polymer flocculant and water are kneaded, or when the plant powder and the polymer flocculant are kneaded, relative to the water The total amount (mass) of the solid content (mass) in the purifier is 1.5 to 8 times the total amount (mass) of the water mixture.

<<Kneading step of plant powder and polymer flocculant>> Although the production method of the aforementioned water purifying agent includes the step of kneading the plant powder and the polymer flocculant, the kneading step specifically includes, for example, the following The steps defined in (a1), (a2) and (b) can be listed in the following three aspects (a1), (a2) and (b). (A1): In the first mixing step, water is mixed with the polymer flocculant to knead the polymer flocculant and water; after that, the second mixing step is performed to mix the plant powder into the kneaded polymer flocculant, To knead the aforementioned plant powder and polymer flocculant. In the above (a1), when the plant powder and the polymer flocculant are kneaded, water may be mixed. In this case, it becomes the following (a2). (A2): In the first mixing step, water is mixed with the polymer flocculant to knead the polymer flocculant and water; after that, the second mixing step is performed to mix the plant powder and water until the kneaded polymer agglomerates Agent to knead the aforementioned plant powder and polymer flocculant. (B): Mixing step, mixing plant powder with polymer flocculant and water for mixing.

In terms of the total amount (mass) of the aforementioned water mixing, in the above (a1), it is called the amount of water mixed in the first kneading step; in the above (a2), it is called the The amount of water mixed in the first kneading step and the amount of water mixed in the second kneading step, the total amount of the two; in the above (b), it is said to be in the kneading step of plant powder and polymer flocculant , The amount of water mixed together when the plant powder and the polymer flocculant are mixed. The total amount (mass) of water mixing is preferably 1.5 times to 8 times relative to the solid content (mass) in the water purifier. Also, in the case of (a2) above, although the total amount of water mixed during the first kneading and the second kneading may be 1.5 to 8 times, the amount of water during the first kneading is relative to the solid content (mass) described above. The mixing amount is preferably at least 1 time or more. In addition, although the solid content in the above water purifier refers to the combination of plant powder and polymer flocculant, if the water purifier also includes the following other than plant powder and polymer flocculant In the case of additives, the solid content in the water purification agent also includes these additives, and the solid content in the water purification agent refers to the combination of all solid components in the water purification agent.

The mixing method is not particularly limited, and can be selected according to the purpose, such as planetary mixer, kneader, butterfly mixer, extruder, etc., as long as it is a mixing machine that can obtain a certain mixing effect, it can be selected. use.

Regarding the rotation speed of the kneader at the time of kneading, it is preferable to perform, for example, in the range of 10 rpm to 180 rpm. Also, for example, under the condition of the rotation speed of 80 rpm to 150 rpm, the total value of the kneading time at the time of kneading is preferably 15 minutes or more and 30 minutes or less. If it is less than 15 minutes, the effect of increasing the viscosity when supplied to the drain water is insufficient. In addition, if it exceeds 30 minutes, the effect of increasing the viscosity when supplied to the drain water also becomes insufficient. If the mixing time is too long, it may be considered that the molecular chain of the polymer flocculant is cut, and the effect of increasing the viscosity is insufficient.

<<Plant powder>> As for the aforementioned plants, any plant that can agglutinate and separate wastes (nickel, copper, fluorine, etc.) in the discharged water is not particularly limited and can be used. For example, for plants having a cation exchange function, for example, changshuohuangma (changshuohuangma), jute (molokheiya), Komatsu cabbage, duck parsley, Japanese turnip, and bok choy are mentioned. Regarding the part of the plant, a part of any one of leaves, stems, and roots can be used. Among the plants, Changshuo jute and jute vegetable are preferred, and more preferably, Changshuo jute, which shows good results in the following examples.

In addition, Changshuo Jute Zhongtejia is "Zhonghuang Ma No. 4" under the identification number 2013 of the Bast Fiber Research Institute of the Chinese Academy of Agricultural Sciences. "Zhonghuang Ma No. 4" has the following characteristics: Type of crop: Jute.

<<Polymer flocculant>> The polymer flocculant is the same as the above-mentioned plant part, and it is not particularly limited as long as it has the effect of removing the aforementioned inorganic waste in the discharged water. Examples include polyacrylamide (PAM), partially hydrolyzed salt of polyacrylamide, sodium alginate, sodium polyacrylate, sodium carboxymethyl cellulose (CMC, Carboxymethyl Cellulose) and the like. Among these, it is preferable to use polyacrylamide. For this polyacrylamide, for example, commercially available products Flopan AN 995SH, FA 920SH, FO 4490, AN 923, AN 956 (manufactured by SNF Co., Ltd.), etc. can be used.

<<Other additives>> As other additives, additives such as fillers, thickeners, colorants, and thixotropic agents may be contained in the water purifying agent. In addition, for the purpose of improving the solubility of the kneading component and water, a small amount of liquid such as alcohol may be contained. In addition, other additives may be added when the polymer flocculant is kneaded, or other additives may be added when the plant powder and the polymer flocculant are kneaded.

<<Particles of plant powder and polymer flocculant>> The mixing ratio of the plant powder particles and the polymer flocculant is preferably in the range of 10:90 to 90:10 by mass ratio. On the surface of the particles obtained by kneading the aforementioned plant powder and the aforementioned polymer flocculant, it is preferable to include a covered part of the plant powder present on the particle surface covered by the polymer flocculant, and a non-coated part that is not covered by the polymer flocculant. part. The median diameter of the aforementioned particles is preferably 150 μm or more, more preferably 150 μm or more and 850 μm or less. If the median diameter of the aforementioned particles is 150 μm or more, the sedimentation of the purification active ingredient is delayed, and the adsorption time of the purification active ingredient can be prolonged. Here, the median diameter (also referred to as d50) refers to the particle size when the particle size of the aforementioned particles is plotted, and the particle size is 50% of the total number in the figure (the larger particle size is compared with the particle size). The smaller diameter side is divided into the same particle size). The median diameter can be measured by a commercially available measuring machine.

<<Other steps>> In addition to the above-mentioned kneading step, the production method of the present invention may also include other steps such as a forming step, a drying step, and a crushing step. Specifically, the particles defined in the present invention are manufactured by a manufacturing method including the following steps: a forming step, forming a shaped body with a kneaded product obtained through the above-mentioned kneading step; and a drying step, forming the aforementioned shaped body Drying; and pulverizing step, pulverizing the dried shaped body. Then, after the aforementioned pulverization step, a classification step may also be included, which is to classify the particles through a sieve.

In the aforementioned shaping step, for example, the aforementioned kneaded product can be shaped by any shaping method to form a shaped body.

In the foregoing drying step, it is preferable to use a multi-stage hot air dryer to dry the obtained molded body at a temperature of 80°C to 150°C and conditions of 2 hours to 12 hours. Preferably, the aforementioned molded body is dried and supplied to the pulverization step. In addition, although the preferable aspect of the aforementioned drying step is to apply the sequence of "drying the molded body obtained in the forming step, and then pulverizing the dried molded body", it is also possible to perform the procedure of "drying the molded body obtained in the forming step". After pulverization, the drying step is performed to obtain particles" in the order. A pulverizer is used in the foregoing pulverization step, for example, a jet type ultrafine pulverizer is used to pulverize particles. In the foregoing classification step, a classifier is used, preferably, for example, a vibrating screen or an air ratio classifier is used to classify the pulverized powder so that the median diameter of the particles is within the desired range. It is better to set the median diameter in the range of 150μm~850μm, so the sieve will only select particles with a particle size in the range of 150μm~850μm, and the powder smaller than 150μm or more than 850μm will be taken out by the sieve and removed (sieved out).

<B; The second aspect of the method for producing a water purifier> In the method for producing a water purifier, before the kneading step of kneading the plant powder and the polymer flocculant, it further includes mixing water with the polymer flocculant and mixing the high The step of mixing the molecular coagulant with water.

<<Kneading step of plant powder and polymer flocculant>> The kneading step in the second aspect is specifically the same as described in (a1) and (a2) above in the first aspect, For example, it includes the steps defined in (a1) and (a2) below, and the following two aspects (a1) and (a2) can be cited. (A1): In the first mixing step, water is mixed with the polymer flocculant to knead the polymer flocculant and water; after that, the second mixing step is performed to mix the plant powder into the kneaded polymer flocculant, To knead the aforementioned plant powder and polymer flocculant. In the above (a1), when the plant powder and the polymer flocculant are kneaded, water may be mixed. In this case, it becomes the following (a2). (A2): In the first mixing step, water is mixed with the polymer flocculant to knead the polymer flocculant and water; after that, the second mixing step is performed to mix the plant powder and water until the kneaded polymer agglomerates Agent to knead the aforementioned plant powder and polymer flocculant.

As defined in the second aspect, pre-kneading the polymer flocculant with water before kneading with the plant powder is effective for obtaining a kneaded system with the desired hardness. At this time, the total amount (mass) of water added during kneading is not particularly limited. For example, the amount of water mixed with respect to the solid content (mass) in the water purifier is 1 time to At 9 times, the water purifying agent for achieving the purpose of the present invention can be obtained. However, as defined in the first aspect, at the time of kneading, the total amount (mass) of water mixing relative to the solid content (mass) in the water purifier is more preferably in the range of 1.5 times to 8 times. Regarding the requirements other than the above-mentioned requirements defined in the kneading step, the content described in the above-mentioned first aspect can be applied.

Regarding the second aspect of ＜＜Plant powder＞＞, ＜＜High polymer flocculant＞＞, ＜＜Other additives＞＞, ＜＜Plant powder and polymer flocculant granules＞＞, ＜＜Other steps＞＞ etc. The requirements can also be applied to the content described in the first aspect.

(Discharge water treatment method) The discharge water treatment method of the present invention dissolves the water purifying agent obtained by the above-mentioned production method of the present invention in water to obtain a dispersion liquid containing plant powder and a polymer flocculant. Next, by supplying the dispersion liquid to the discharged water containing inorganic wastes, the inorganic wastes in the discharged water are removed. The aforementioned inorganic waste includes, for example, inorganic waste having at least one selected from the group consisting of nickel, fluorine, iron, copper, zinc, chromium, arsenic, cadmium, and lead. As for the aforementioned dispersion, in addition to pure water (distilled water), water with a conductivity of 30 μS/cm or more can be used. In this way, cheaper tap water and underground water can be used. Even if tap water and underground water are used for the dispersion, the concentration of inorganic ions in the discharged water can be reduced to a concentration below the desired concentration, and it exhibits excellent water purification performance. The water purifier obtained by the production method of the present invention is used to prepare a dispersion.

The discharge water treatment method of the present invention will be specifically described. For example, alkali can also be added to the discharged water to make the discharged water alkaline to insolubilize at least a part of the aforementioned heavy metal ions, and after the insolubilization step of forming a suspended solid, add the manufacturing method of the present invention The obtained water purifying agent. Furthermore, after separately adding a polymer flocculant such as amine, the water purifying agent obtained by the production method of the present invention may be added. It is preferable to use the water purifying agent obtained by the manufacturing method of the present invention to prepare a dispersion liquid, and supply the dispersion liquid to the drain water. By supplying the dispersion to the discharged water, the inorganic wastes are aggregated and settled, and the sediment separated by the sedimentation is removed to purify the discharged water.

[Examples] Hereinafter, although examples of the present invention will be described, the present invention is not limited to these examples.

(Example 1) Nickel sulfate hexahydrate was dissolved in pure water, and 800 g of an aqueous solution containing 50 mg/L of nickel ions was produced, which was used as the discharge water (hypothetical discharge water) used in the experiment. Next, sodium hydroxide was supplied to the above-mentioned drain water so that the pH value became 10, and stirred to insolubilize nickel. The nickel ion concentration of the supernatant liquid of the discharged water was 2 mg/L. <Water Purifier> Furthermore, "Concentrated Spinach from Maebashi, Gunma Prefecture" is used as the plant, and polypropylene amide (PAM) is used as the polymer flocculant. The pellet 1 is obtained by the manufacturing method shown below, and this pellet 1 is used as the water purifying agent 1.

＜＜Method for manufacturing water purifier＞＞ Add 5 times the mass of water to the mass of the total solid content of the plant powder and polymer flocculant to obtain a kneaded product (plant powder + polymer flocculant + water = 30kg), The kneaded product was put into a planetary mixer (manufactured by Aikosha Manufacturing Co., Ltd., mixer ACM-110, capacity 110L), and kneaded by applying shear stress under mixing conditions of 150 rpm and 20 minutes. The obtained kneaded product is shaped, and a shaped body is produced. Using a multi-stage hot air dryer (a rack oven device manufactured by Shichiyo Manufacturing Co., Ltd.), the molded product was dried at 120°C for 3 hours, and then at 150°C for 2 hours. Next, the dried flakes were pulverized with an airflow type ultrafine pulverizer (Ceren Miller manufactured by Masuko Sangyo Co., Ltd.) so that the median diameter was 400 μm. Furthermore, the median diameter was measured by mastersizer2000 (manufactured by Malvern Instrument). Use a classifier (vibrating sieving machine manufactured by Mikasa Co., Ltd.) and set it to only siev the powder with a particle size in the range of 150μm~850μm. The particles with a particle size of less than 150μm or a particle size of more than 850μm are sieved. Take out and remove (sieve out). In this way, particles 1 are obtained and used as water purifiers 1.

<Dispersion> To the particles, water with a conductivity of 110 μS/cm (tap water from Kanuma City, Tochigi Prefecture) was added and stirred so that the solid content became 0.1% by mass to obtain a dispersion liquid 1.

<Characteristic evaluation> Next, the dispersion liquid 1 containing the water purifying agent 1 was added to the above-mentioned drain water, and the solid content was adjusted to 7 mg/L, and it stirred. Here, the "solid content" measurement method can be obtained by measuring the slurry concentration of the discharged water using a moisture meter and deducing the solid content. The drain water to which the dispersion liquid 1 was added was transferred to a sedimentation tank, and after that, it was allowed to stand, and the state was visually confirmed every 1 hour. The time at which two layers of the supernatant clear liquid and the sediment were confirmed to be clearly separated was measured as the settling time. In addition, the supernatant liquid was taken out and the ion concentration was measured with Lambda (Λ)9000 (manufactured by Kyoritsu Rikaki Lab). The following criteria were used to evaluate the water purification performance of the results. [Evaluation criteria for water purification performance] ◎: Less than 1.0 mg/L (below the detection limit) ○: 1.0 mg/L or more and less than 1.4 mg/L ○△: 1.4 mg/L or more and less than 1.7 mg/L △: 1.7 mg/L or more and less than 2.0 mg/L ╳: 2.0 mg/L or more The evaluation results of Example 1 are shown in Table 1-1. In addition, Table 1-1 also shows the result of the dispersion viscosity 50 (mPa‧sec) measured by the B-type viscosity agent. In addition, with regard to the hardness of the kneaded product obtained in the process of manufacturing the pellets, the measurement result in the AR-G2 hardness measurement mode manufactured by TA Instruments is also displayed according to the above-mentioned method. In addition, the above-mentioned viscosity measurement was measured with a Toki Sangyo TVC-7 viscometer (B-type viscometer) at a room temperature of 23°C using a No. 1 rotor. In addition, in Table 1-1, plant powder 1 refers to “concentrated spinach produced in Maebashi, Gunma Prefecture”, and PAM refers to polyacrylamide (the same applies to Table 1-2 to Table 1-3, and Table 2).

(Example 2) Granules 2 were produced in the same manner as in Example 1, except that the plant used in Example 1 was changed to Changshuo jute (produced in Guangzhou, China) and the rotation speed of the mixer in the kneading step was changed to 80 rpm. Using the water purifying agent 2 made of pellets 2, and in the same manner as in Example 1, the characteristics of the water purifying agent were evaluated. The evaluation results of Example 2 are shown in Table 1-1. In addition, the plant powder 2 in Table 1-1 refers to "Changshuo Jute (produced in Guangzhou, China)".

(Example 3) As an alternative to the plant of Example 2, "Zhonghuang Ma No. 4" of the ID No. 2013 of the Chinese Academy of Agricultural Sciences Bast Research Institute of Changshuo Jute was used. Except for this, pellets 3 were produced in the same manner as in Example 2. Using the water purifying agent 3 made of pellets 3, and in the same manner as in Example 1, the characteristics of the water purifying agent were evaluated. The evaluation results of Example 3 are shown in Table 1-1. In addition, the plant powder 3 in Table 1-1 refers to "Zhonghuang Ma No. 4".

(Example 4) A pellet 4 was produced in the same manner as in Example 3 except that the amount of water added to the solid content (polymer aggregation + plant powder) in Example 3 was changed to three times. Using the water purifying agent 4 made of pellets 4, and in the same manner as in Example 1, the characteristics of the water purifying agent were evaluated. The evaluation results of Example 4 are shown in Table 1-1.

(Example 5) A pellet 5 was produced in the same manner as in Example 3 except that the amount of water added to the solid content (polymer aggregation + plant powder) in Example 3 was changed to 8 times. Using the water purifying agent 5 made of the pellets 5, and in the same manner as in Example 1, the characteristics of the water purifying agent were evaluated. The evaluation results of Example 5 are shown in Table 1-1.

(Example 6) Pellet 6 was produced in the same manner as in Example 3 except that the kneading time of the kneading step in Example 3 was changed to 15 minutes. Using the water purifying agent 6 made of pellets 6, and in the same manner as in Example 1, the characteristics of the water purifying agent were evaluated. The evaluation results of Example 6 are shown in Table 1-2.

(Example 7) Pellet 7 was produced in the same manner as in Example 3 except that the kneading time of the kneading step in Example 3 was changed to 30 minutes. Using the water purifying agent 7 made of pellets 7, and in the same manner as in Example 1, the characteristics of the water purifying agent were evaluated. The evaluation results of Example 7 are shown in Table 1-2.

(Example 8) The pellet 8 was produced in the same manner as in Example 3 except that the water as the dispersion in Example 3 was changed to water with a conductivity of 198 μS/cm (tap water in Kanuma City, Tochigi Prefecture). Using the water purifying agent 8 made of pellets 8, and in the same manner as in Example 1, the characteristics of the water purifying agent were evaluated. The evaluation results of Example 8 are shown in Table 1-2.

(Example 9) Granules 9 were produced in the same manner as in Example 3 except that the water as the dispersion in Example 3 was changed to water with a conductivity of 30 μS/cm obtained by mixing appropriate amounts of Kanuma City, Tochigi Prefecture tap water and distilled water. Using the water purifying agent 9 made of pellets 9, and in the same manner as in Example 1, the characteristics of the water purifying agent were evaluated. The evaluation results of Example 9 are shown in Table 1-2.

(Example 10) A pellet 10 was produced in the same manner as in Example 3 except that the classification step of Example 3 was not performed. Using the water purifying agent 10 made of pellets 10, and in the same manner as in Example 1, the characteristics of the water purifying agent were evaluated. The evaluation results of Example 10 are shown in Table 1-2.

(Example 11) A pellet 11 was produced in the same manner as in Example 3 except that the polymer flocculant of Example 3 was changed to polyamine. Using the water purifying agent 11 made of pellets 11, and in the same manner as in Example 1, the characteristics of the water purifying agent were evaluated. The evaluation results of Example 11 are shown in Table 1-2.

(Example 12) Potassium fluoride was dissolved in pure water, and 800 g of an aqueous solution containing 2,500 mg/L of fluoride ions was produced, which was used as drain water for experiments (hypothetical drain water). Next, 8.6 mg/L of calcium chloride was added to the above-mentioned drain water, and sodium hydroxide was added to make the pH value 7.5 to 9.0, and while stirring, the fluorine was insolubilized. By this operation, the supernatant liquid containing the micro-flock in the fluorine aqueous solution is separated from the sediment. At this point, the ion concentration of the upper clear liquid of the discharged water was 10 mg/L. Except for using the above-mentioned discharged water, in the same manner as in Example 3, the water purifying agent 3 made of pellets 3 was used, and the characteristics of the water purifying agent were evaluated. The evaluation results of Example 12 are shown in Table 1-3.

(Example 13) The ferric chloride hexahydrate was dissolved in pure water, and 800 g of an aqueous solution containing 200 mg/L of iron ions was prepared as the drain water (hypothetical drain water) used in the experiment. Furthermore, while adding sodium hydroxide to the above-mentioned drain water to make the pH value 6.5 to 9.0, stirring was carried out to insolubilize iron. At this point, the ion concentration of the upper clear liquid of the discharged water was 2 mg/L. Except for using the above-mentioned discharged water, in the same manner as in Example 3, the water purifying agent 3 made of pellets 3 was used, and the characteristics of the water purifying agent were evaluated. The evaluation results of Example 13 are shown in Table 1-3.

(Example 14) The copper sulfate pentahydrate was dissolved in pure water, and 800 g of an aqueous solution containing 100 mg/L of copper ions was produced, which was used as the discharge water (hypothetical discharge water) used in the experiment. Furthermore, while adding sodium hydroxide to the drain water to have a pH of 7.0 to 8.0, stirring was carried out to insolubilize copper. At this point, the ion concentration of the upper clear liquid of the discharged water was 2 mg/L. Except for using the above-mentioned discharged water, in the same manner as in Example 3, the water purifying agent 3 made of pellets 3 was used, and the characteristics of the water purifying agent were evaluated. The evaluation results of Example 14 are shown in Table 1-3.

(Example 15) Zinc nitrate hexahydrate was dissolved in pure water, and 800 g of an aqueous solution containing 100 mg/L of zinc ions was produced, which was used as the discharge water for the experiment (hypothetical discharge water). Furthermore, while adding sodium hydroxide to the drain water to have a pH of 9.0 to 9.5, stirring was performed to insolubilize zinc. At this point, the ion concentration of the upper clear liquid of the discharged water was 5 mg/L. Except for using the above-mentioned discharged water, in the same manner as in Example 3, the water purifying agent 3 made of pellets 3 was used, and the characteristics of the water purifying agent were evaluated. The evaluation results of Example 15 are shown in Table 1-3.

(Example 16) Potassium dichromate was dissolved in pure water, and 800 g of an aqueous solution containing 100 mg/L of chromium ions was made, which was used as drain water for the experiment (hypothetical drain water). Furthermore, while adding sodium hydroxide to the drain water to have a pH of 6.0 to 7.5, it was stirred to insolubilize chromium. At this point, the ion concentration of the upper clear liquid of the discharged water was 5 mg/L. Except for using the above-mentioned discharged water, in the same manner as in Example 3, the water purifying agent 3 made of pellets 3 was used, and the characteristics of the water purifying agent were evaluated. The evaluation results of Example 16 are shown in Table 1-3.

(Example 17) Arsenic trioxide was dissolved in pure water, and 800 g of an aqueous solution containing 10 mg/L of arsenic ions was made, which was used as drain water for experiments (hypothetical drain water). Next, 65 mg/L of iron chloride and 354 mg/L of calcium chloride were added to the drain water, and then sodium hydroxide was added to make the pH value 8.0 to 9.5, and while stirring, the arsenic was insolubilized. At this point, the ion concentration of the upper clear liquid of the discharged water was 0.05 mg/L. Except for using the above-mentioned discharged water, in the same manner as in Example 3, the water purifying agent 3 made of pellets 3 was used, and the characteristics of the water purifying agent were evaluated. The evaluation results of Example 17 are shown in Table 1-3. However, in Example 17, after the sedimentation time was measured in the same manner as in Example 3, the supernatant liquid was taken out and the volume was concentrated to 1/100 by an evaporator, and the ion concentration was measured. Regarding arsenic ions, if the ion concentration is judged to be a good result of 0.01 mg/L or less, the result is evaluated as ⓞ.

[Table 1-1]

[Table 1-2]

[Table 1-3]

(Example 18) Regarding the water purifiers 3, 4, and 5 obtained in Examples 3, 4, and 5, the same method as in Examples 3, 4, and 5 was used to replace the water in the dispersion with conductivity. Evaluation of the characteristics of water purifiers with 1μS/cm of water (distilled water). The evaluation results when using distilled water as the water of the dispersion of the water purifiers 3, 4, and 5 are the same as the water with conductivity of 110 μS/cm (tap water from Kanuma City, Tochigi Prefecture) performed in Examples 3, 4, and 5 above. The evaluation results at the time of use of the dispersion are shown in Table 2 together.

(Comparative Examples 1 to 2) In Example 3, except that the amount of water added to the solid content (polymer aggregate + plant powder) was changed to 0.8 times and 9 times, the same procedure as in Example 3 was carried out to produce comparative particles 1 ~2. Using comparative water purifiers 1 and 2 made of comparative particles 1 and 2, and the same as in Example 3 and Example 18, when using water with a conductivity of 110 μS/cm (tap water in Kanuma City, Tochigi Prefecture) as the dispersion liquid, And when using distilled water with a conductivity of 1 μS/cm as the dispersion liquid, the water purification performance of the discharged water was evaluated. Table 2 shows the evaluation results of Comparative Examples 1-2. In addition, with respect to the comparative particles 1 used in Comparative Example 1, although it is also intended to measure the hardness of the kneaded material obtained in the manufacturing process by the same method as in Example 1, it is because the kneaded material has no stickiness. It disintegrates into pieces and does not form lumps, so it cannot be measured with a hardness meter.

[Table 2]

(Example 19) Using the dispersion liquid as in Example 3, the experiment for evaluating the purification performance of discharged water in Example 3 was performed 30 times. On the other hand, using the water purifying agent 3 obtained in Example 3, instead of using a dispersion liquid, the water purifying agent 3 was directly put into the above-mentioned drainage, and an experiment for evaluating the purification performance of the discharged water was performed 30 times. The addition amount of the water purifying agent 3 is an amount such that the solid content becomes 7 mg/L with respect to the discharged water. The variability of purification performance was evaluated based on the results of each experiment. In the case of using the dispersion, the result was ⊚, and it was confirmed that the purification result with little fluctuation was obtained every time. On the other hand, when the water purifier is directly put into the discharged water, although there are cases where good results are shown as ◎, there are cases where the same results are not shown (when there are results of ○ or ○△), but because it is used The experiment is carried out in the same way, so the experimental results are subject to variability.

(Example 20) The pellet 20 was produced in the same manner as in Example 3 except that the kneading step in Example 3 was changed as shown below. Using the water purifying agent 20 made of particles 20, and in the same manner as in Example 3, the characteristics of the water purifying agent were evaluated. <Kneading step> The amount of water shown in Table 3 below was added to the polymer flocculant, and the polymer flocculant and water were kneaded for 10 minutes. After that, the plant powder is mixed with the kneaded polymer flocculant, and the plant powder and the polymer flocculant are kneaded for 10 minutes. Furthermore, using the water purifying agent 20 obtained by the above-mentioned method, as shown in Example 18, the characteristics of the water purifying agent when the water of the dispersion was changed to water with a conductivity of 1 μS/cm (distilled water) were evaluated. Table 3 shows the results of the evaluation using the water purifier 20.

(Examples 21-23) Except having changed the water purifier 20 to the conditions shown in the following Table 3, the water purifier 21-23 was produced by the same method. In Example 20, the characteristics of the water purification agent were evaluated by the same method except that the water purification agent 20 was changed to the water purification agents 21 to 23 (Examples 21 to 23).

[table 3]

In summary, from the results of Examples 1 to 23, it can be confirmed that the water purifier system manufactured by the manufacturing method of the present invention can be applied to the water purifier when the size of the drain tank is used in a large automatic purification device. , And it is low-cost and shows stable purification performance unchanged every time.

none

none.

Claims (13)

A method for producing a water purifying agent, which is a method for producing a water purifying agent made of particles containing plant powder and a polymer flocculant, which comprises: a kneading step of kneading the plant powder and the polymer flocculant; wherein In the aforementioned kneading step, the hardness of the kneaded product obtained through the aforementioned kneading step is to knead the plant powder and polymer agglomeration in such a way ^{that the stress is 3N/mm 2} ~ 100N/mm ^{2 under the following measurement conditions} Measurement conditions: For the aforementioned mixture, use a stress-controlled rheometer (viscosity measuring device) to measure the stress when a probe with a diameter of 16mm is pushed in at a speed of 30mm/min and a pushing amount is 5mm. The method for producing a water purifier according to claim 1, wherein any of the following (a1), the following (a2), and the following (b) are met: (a1): the first kneading step, Water is mixed with the polymer flocculant to knead the polymer flocculant and water; after that, the second mixing step is performed to mix the plant powder with the kneaded polymer flocculant to knead the plant powder and the polymer A flocculant; wherein, in the first kneading step, the total amount (mass) of water mixing relative to the solid content (mass) in the water purifying agent is 1.5 to 8 times; (a2): the first kneading step , Water is mixed with the aforementioned polymer flocculant to knead the aforementioned polymer flocculant and water; after that, a second mixing step is carried out, the aforementioned plant powder and water are mixed into the aforementioned polymer flocculant to knead the aforementioned plant Powder and polymer flocculant; wherein, in the first kneading step and the second kneading step, the total amount (mass) of water mixed with respect to the solid content (mass) in the water purifier is 1.5 times to 8 And (b): mixing step, mixing plant powder with polymer flocculant and water to knead it; wherein, in the aforementioned mixing step, the water is mixed with respect to the solid content (mass) in the aforementioned water purifying agent The total amount (quality) is 1.5 times to 8 times. The method for producing a water purifying agent according to claim 1, which comprises: a first kneading step, mixing water with the polymer flocculant to knead the polymer flocculant and water; then, performing a second kneading step , Mixing the plant powder with the kneaded polymer flocculant to knead the plant powder and the polymer flocculant. The method for producing a water purifier according to claim 1, wherein the total value of the kneading time during the kneading is 15 minutes or more and within 30 minutes under the condition of a rotation speed of 80 rpm to 150 rpm. The method for producing a water purifying agent according to claim 1, wherein the plant powder is selected from any one of the group consisting of Changshu jute, jute, Komatsu cabbage, Japanese celery, Japanese turnip, and bok choy. The method for producing a water purifying agent according to claim 5, wherein the plant powder is Changshuo jute. The method for manufacturing a water purifying agent according to claim 6, wherein the aforementioned Changshuo jute is "Zhonghuang Ma No. 4" under the identification number 2013 of the Bast Fiber Research Institute of the Chinese Academy of Agricultural Sciences. The method for producing a water purifying agent according to claim 1, wherein the median diameter of the water purifying agent is 150 μm or more and 850 μm or less. The method for producing a water purifying agent according to claim 1, wherein the polymer flocculant is polyacrylamide. The method for producing a water purifying agent according to claim 1, which comprises: a forming step of forming a shaped body with a kneaded product obtained through the aforementioned kneading step; a drying step of drying the aforementioned shaped body; and a pulverizing step, The dried shaped body is pulverized. A method for treating discharged water, which dissolves the water purifier obtained by the method for producing a water purifier as set forth in any one of claims 1 to 10 in water to obtain a plant powder and a polymer coagulant Then, by supplying the dispersion liquid to the discharged water containing inorganic wastes, the inorganic wastes in the discharged water are removed. The discharge water treatment method according to claim 11, wherein the discharge water system has at least one inorganic waste selected from the group consisting of nickel, fluorine, iron, copper, zinc, chromium, arsenic, cadmium, and lead . The method for treating discharged water according to claim 11, wherein the conductivity of the water in the dispersion liquid is 30 μS/cm or more.