TW201822861A - Method for producing water-purifying agent and method for treating wastewater - Google Patents

Abstract

A production method for a water-purifying agent that comprises a granulated substance that contains a plant powder and a polymer coagulant. The production method is characterized by including a step for mixing and kneading the plant powder and the polymer coagulant such that the hardness of the kneaded mixture obtained by means of the mixing and kneading demonstrates a stress of 3-100 N/mm2 under the following measurement conditions: a stress-controlled rheometer (a viscosity measurement device) is used to measure the stress at a push depth of 5 mm when a probe that has a diameter of 16 mm is pushed into the kneaded mixture at a pushing speed of 30 mm/min.

Description

Method for manufacturing water purification agent and method for treating discharged water

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

In recent years, in the process of manufacturing various products in factories, a large amount of waste liquid containing environmentally harmful substances such as metal ions or inorganic ions has been produced. On the other hand, regulations regarding the emission of these inorganic ions have gradually become stricter. In order to comply with such discharge regulations, the present inventors sought a method for removing inorganic ions that can efficiently remove inorganic ions from the discharged water containing the inorganic ions, and implement it as simply and cost-effectively as possible. Concerning methods for removing impurities such as water discharged from factories, agglutination precipitation methods, ion exchange methods, adsorption methods using adsorbents such as activated carbon, electro-adsorption methods, and magnetic adsorption methods have been proposed.

For example, in the case of the agglutination precipitation method, a method has been proposed, which comprises adding alkali to the discharged water in which heavy metal ions are dissolved and making the discharged water alkaline, and then insolating at least a part of the heavy metal ions. A step of forming a suspended solid; a step of adding an inorganic agglutinating agent to the discharged water to coagulate and settle the suspended solid; and passing the discharged water through a leafy vegetable containing jute (mulukhiya) and komatsuna An adsorption step of an adsorption layer of a cation exchanger (for example, refer to Patent Document 1). At the same time, an agglutination method has also been proposed, which involves mixing or using agglutinating agents containing at least any one of jute, its dried products, or extracts thereof, and polymer agglutinating agents, thereby aggregating fine particles in suspension Separation (for example, refer to Patent Document 2).

In addition, when the amount of discharged water to be purified is larger, the amount of unnecessary substances contained in the discharged water is larger, or the types of unnecessary substances contained in the discharged water are more, it is desirable to construct a type of such discharged water A system that automatically puts in necessary purification agents during the purification process. In addition to performing a high-speed and stable purification process, automation of the device is an important issue, and in addition to providing an automatic purification device showing stable purification performance, it is also desirable to provide a water purification agent suitable for the automatic purification device. However, the methods described in the above-mentioned Patent Documents 1 and 2 are not aware of an automatic device for purifying the discharged water, and the water-purifying agents described in these documents are not suitable for supplying water-purifying agents to automated system devices. Therefore, a water purification agent composed of particles of a mixture of a plant powder and a polymer coagulant has been proposed as a water purification agent that can be suitably used in an automatic purification device (for example, refer to Patent Document 3).

[Prior Art Literature] [Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 2011-194385 [Patent Literature 2] Japanese Patent Laid-Open No. 11-114313 [Patent Literature 3] Japanese Patent Laid-Open No. 2016-73898

[Problems to be Solved by the Invention] However, when the size of the automatic purification device is increased, 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. In terms of purification performance, I understand that the water purification agent contained in the above-mentioned Patent Document 3 is insufficient. Therefore, the present inventors desire to provide a water purifying agent which is also applicable to a water purifying agent having a size of a drain tank used in a large automatic purification device, and which is stable at low cost and capable of being displayed without change each time. Purification performance.

The present invention solves a plurality of problems in the past, and has as its object to achieve the following objects. That is, the object of the present invention is to provide a water purifying agent, which can also be applied to a water purifying agent having a size of a drain tank for a large automatic purification device, and is low-cost and can be displayed without changing each time. 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 composed of particles of a plant powder and a polymer agglutinating agent, which includes: a kneading step, mixing the plant powder with high Molecular agglutination kneading; wherein, in the kneading step, the hardness of the kneaded material obtained through the kneading step is kneaded in such a manner that the stress is displayed as 3N / mm ² to 100N / mm ² under the following measurement conditions. Plant powder and polymer agglutinating agent; Measurement conditions: For the aforementioned kneaded material, a stress-controlled rheometer (viscosity measuring device) is used to measure the insertion amount when a probe with a diameter of 16 mm is inserted at a speed of 30 mm / min. Stress at 5mm. <2> The manufacturing method of the water purification agent as described in said <1> which is compatible with any one of the following (a1), (a2), and (b): (a1): 1st In the kneading step, water is mixed to the aforementioned polymer agglutinating agent to knead the aforementioned polymer agglutinating agent and water; and then, a second kneading step is performed to mix the aforementioned plant powder to the kneaded polymer agglomerating agent to knead the plant Powder and polymer coagulant; wherein, in the first kneading step, the total amount (mass) of water mixing is 1.5 to 8 times the solid content (mass) in the water purifying agent; (a2): A first kneading step, mixing water to the polymer coagulant to knead the polymer coagulant and water; and then performing a second kneading step, mixing the plant powder and water to the kneaded polymer coagulant, The above-mentioned plant powder and polymer agglutinating agent are kneaded; wherein, in the first kneading step and the second kneading step, the total amount of water mixing with respect to the solid content (mass) in the water purifying agent. Mass) is 1.5 times to 8 times; and (b): a kneading step in which the plant powder is mixed with a polymer coagulant and water to knead it; wherein, in the kneading step, compared with the solid in the water purifying agent, The composition (mass) and the total amount (mass) of water mixing are 1.5 to 8 times. <3> The method for producing a water purification agent according to the above <1>, comprising: a first kneading step, mixing water to the polymer agglutinating agent to knead the polymer agglutinating agent and water; and then, performing In a second kneading step, the plant powder is mixed with the kneaded polymer aggregate agent to knead the plant powder and the polymer aggregate agent. <4> The method for producing a water purifying agent according to any one of <1> to <3>, wherein the total value of the kneading time during the 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 according to any one of <1> to <4>, wherein the plant powder is selected from the group consisting of changshuohuangma, jute, komatsu, and duck parsley , Japanese turnips and wave dishes. <6> The method for producing a water purifying agent according to the above <5>, wherein the plant powder is Changshuo jute. <7> The method for producing a water purifying agent according to the above <6>, wherein the Changshuo jute is an identification number 2013 of "Medium Jute 4" of the Institute of Hemp Research, Chinese Academy of Agricultural Sciences. <8> The manufacturing method of the water purification agent as described in any one of said <1>-<7> whose median diameter of this water purification agent is 150 micrometers or more. <9> The method for producing a water purification agent according to any one of <1> to <8>, wherein the polymer agglutinating agent is polypropylene amidamine. <10> The method for producing a water purifying agent according to any one of the above <1> to <9>, comprising: a forming step of forming a formed body obtained by forming the kneaded material obtained through the kneading step; drying A step of drying the aforementioned compact; and a crushing step of crushing the dried compact. <11> A method for treating discharged water, which is obtained by dissolving a water purifying agent obtained by the water purifying agent manufacturing method described in any one of the aforementioned <1> to <10> in water, thereby obtaining a plant powder and a high The dispersion liquid of the molecular coagulant is then supplied to the discharged water containing the inorganic waste to remove the inorganic waste from the discharged water. <12> The method for treating discharged water according to the above <11>, wherein the discharged water is at least one selected from the group consisting of nickel, fluorine, iron, copper, zinc, chromium, arsenic, cadmium, and lead. Inorganic waste. <13> The method for treating discharged water according to the above <11> or <12>, wherein the conductivity of water in the dispersion is 30 μS / cm or more.

[Effects of the Invention] According to the present invention, a plurality of problems in the past can be solved and the foregoing objects can be achieved, and a water purification agent can be provided, which can also be applied when the size of the drain tank is used for a large automatic purification device Water purification agent, and it is a low-cost and can display stable purification performance that does not change every time.

(Manufacturing method of water purification agent) The water purification agent manufactured by the manufacturing method of the water purification agent of this invention (henceforth the manufacturing method of this invention) is a particle | grain containing a plant powder and a polymer aggregating agent. The manufacturing method of the present invention includes a kneading step of kneading a plant powder and a polymer agglutinating agent, and further includes a forming step, a drying step, a pulverizing step, and other steps as necessary. The manufacturing method of the present invention is characterized in that in the kneading step, the hardness of the kneaded material obtained through the kneading step is such that the stress is displayed as 3 N / mm ² to 100 N / mm ² under the following measurement conditions. To mix plant powder and polymer agglutinating agent. Measurement conditions: For the aforementioned kneaded material, a stress-controlled rheometer (viscosity measuring device) was used to measure the stress at a pushing speed of 30 mm / min and a probe with a diameter of 16 mm when the pushing amount was 5 mm.

After the kneaded product having the desired hardness is obtained, the following production method is more preferable. The manufacturing method of the present invention defines a total amount (mass) of water mixing when kneading a polymer coagulant and water, or when kneading a plant powder and a polymer coagulant. The total amount (mass) of the water mixture is 1.5 to 8 times the solid content (mass) in the water purifying agent. In addition, the manufacturing method of the present invention defines a kneading step of mixing water with the polymer agglutinating agent and kneading the polymer agglutinating agent and water before the kneading step of the plant powder and the polymer agglutinating agent. The water purifying agent manufactured by the manufacturing method of the present invention satisfying the above-mentioned requirements can be applied to a water purifying agent having a size of a drain tank for a large automatic purification device, and is low-cost and can be displayed without change every time. Water purification agent with stable purification performance.

When the water purification agent is used to purify the discharged water, the method of adding the water purification agent includes a method of directly pouring the water purification agent into the discharged water, and dissolving the water purification agent in water to obtain plant powder and A method of dispersing a polymer coagulant, and then pouring the dispersion into drained water. However, if the size of the automatic purification device becomes large, especially when the size of the drain tank becomes large, in the case of a granular water purification agent, a stable and uniform dispersion state is formed every time and the water purification performance is maintained without change. This department becomes difficult. Therefore, in an automatic purification apparatus having a large size of a drain tank, it becomes necessary to utilize a purification method of drain water using a dispersion liquid. Therefore, the present inventors conducted repeated researches on the purification treatment of the discharged water using the dispersion liquid, and found that, depending on the type of water in the dispersion liquid, the viscosity of the dispersion liquid changed when the plant powder and the polymer coagulant were dissolved. Then, the present inventors obtained the following insight: the difference in the viscosity of the dispersion liquid will affect the purification performance of the discharged water, and in order to obtain a good purification performance, it is effective to increase the viscosity of the dispersion liquid to some extent. Specifically, although tap water and groundwater are typically cheaper, in the case where a dispersion liquid is obtained by using water having high conductivity due to the influence of ions and the like, if the dispersion liquid is added to the discharged water, , The viscosity of the discharged water becomes small, and the solid components such as plant powder settle in a short time. As a result, sufficient inorganic ion adsorption performance cannot be obtained. On the other hand, as a substitute for tap water and groundwater, such a problem does not occur if distilled water with low conductivity is used. However, distilled water is expensive, and semiconductor factories, electroplating factories, etc., which process a large amount of discharged water every day, have become a heavy burden. Therefore, when the present inventors conducted further research, they found that a water purifying agent 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 cheaper, as a dispersion. Up to the concentration below.

The inventors then realized that the effect of increasing the viscosity even with the dispersion of tap water and groundwater is due to the adjustment and mixing of plant powder and polymer agglutinating agent in the method of manufacturing water purification agents. The hardness of the obtained kneaded material was effective. Here, the hardness of the kneaded material can be determined using the AR-G2 hardness measurement mode made by TA Instruments, which is a stress-controlled rheometer (viscosity measuring device). Specifically, about 7.5 g of the kneaded product was filled in a polypropylene cylindrical container with an inner diameter of 22 mm and a depth of 11 mm. Using a probe with a diameter of 16 mm, it was measured at a pushing speed of 30 mm / min. The stress when the pushing amount is 5mm. In the present invention, the stress measured under these conditions is called "hardness". As a result, the hardness of the kneaded material is preferably in a range of ³ N / mm ² to 100 N / mm ² . Next, the present inventors have found that it is important to perform the steps shown in (i) or (ii) below in order to obtain a kneaded product having the desired hardness. (I) In the method for manufacturing a water purifying agent, when the polymer agglutinating agent and water are kneaded, or when the plant powder and the polymer agglutinating agent are kneaded, the water is mixed with respect to the solid content (mass) in the water purifying agent. The total amount (mass) is 1.5 times to 8 times. (Ii) In the method for manufacturing a water purifying agent, before the kneading step of kneading the plant powder and the polymer coagulant, a kneading step of mixing water to the polymer coagulant and kneading the polymer coagulant and water is performed.

In this way, if the polymer coagulant is added with a large amount of water and kneaded, or the polymer coagulant and water are kneaded in advance before kneading with the plant powder, a kneaded product having a desired hardness can be formed. Moreover, the water purifying agent manufactured through such a kneaded product can increase the viscosity of the dispersion liquid in which the water purifying agent is dispersed and the viscosity of the discharged water after the dispersion liquid is injected. Although the reason is not clear, it can be considered as follows: Under these conditions, whether to agglomerate the molecular chain of the polymer agglutination agent to some extent, and to improve its solubility with water Make effective contributions.

In the following, the specific configuration of the water purification agent manufacturing method is divided into (A) a first aspect and (B) a second aspect and described in detail.

<A; First aspect of the water purifying agent manufacturing method> In the aforementioned water purifying agent manufacturing method, when the polymer agglutinating agent and water are kneaded, or when the plant powder and the polymer agglutinating agent are kneaded, compared with the water, The solid content (mass) in the purifying agent is 1.5 times to 8 times the total amount (mass) of the water mixture.

<< Kneading steps of plant powder and polymer agglutinating agent> Although the aforementioned method for producing a water purifying agent includes a step of kneading a plant powder and a polymer agglutinating agent, the kneading step specifically includes, for example, the following The steps defined in (a1), (a2), and (b) can be exemplified by the following three aspects (a1), (a2), and (b). (A1): a first kneading step, mixing water to a polymer coagulant to knead the polymer coagulant and water; and then, performing a second kneading step, mixing the plant powder to the kneaded polymer coagulant, To knead the aforementioned plant powder and polymer agglutinating agent. In the above (a1), when the plant powder and the polymer coagulant are kneaded, water may be mixed, and in this case, the following (a2) is obtained. (A2): the first kneading step, mixing water to the polymer coagulant to knead the polymer coagulant and water; and then, performing the second kneading step, mixing the plant powder and water to the kneaded polymer coagulant Agent to knead the aforementioned plant powder and polymer agglutinating agent. (B): kneading step, mixing plant powder with polymer coagulant and water to knead it.

Regarding the total amount (mass) of the aforementioned water mixing, in the above (a1), it is referred to as the amount of water mixing in the first kneading step; in the above (a2), it is referred to as the first The amount of water mixed in the first kneading step and the amount of water mixed in the second kneading step, the total of the two; in (b) above, it is referred to as the kneading step of the plant powder and the polymer agglutinating agent. The amount of water that is mixed together when the plant powder is mixed with the polymer coagulant. The total amount (mass) of the water mixture is preferably 1.5 to 8 times the solid content (mass) in the water purifying agent. In addition, in the case of (a2), although the total amount of water mixing during the first kneading and the second kneading may be 1.5 times to 8 times, the water content during the first kneading is relative to the solid content (mass). The amount of mixing is preferably at least 1 time or more. In addition, although the solid content in the water purifying agent refers to a combination of a plant powder and a polymer agglutinating agent, if the water purifying agent further includes a plant powder and a polymer agglutinating agent, the following are shown. In the case of additives, the solid ingredients in the water purifying agent also include these additives. The solid ingredients in the water purifying agent refer to a combination of all solid ingredients in the water purifying agent.

As for the kneading means, it 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 kneading machine that can obtain a certain kneading effect, it can be used. use.

The rotation speed of the kneader during the kneading is preferably performed in a range of 10 rpm to 180 rpm, for example. In addition, for example, under the condition that the rotation speed is 80 rpm to 150 rpm, the total value of the kneading time during the kneading is preferably 15 minutes or more and 30 minutes or less. If it is less than 15 minutes, the effect of increasing viscosity when supplied to the drain water is insufficient. If it exceeds 30 minutes, the effect of increasing the viscosity when supplying to the drain water becomes insufficient. If the kneading time is too long, it may be considered that the molecular chain of the polymer agglutinating agent is cut, and the effect of increasing the viscosity is insufficient.

<< Plant powder >> As long as the plant is a plant capable of aggregating and separating wastes (nickel, copper, fluorine, etc.) in the discharged water, it is not particularly limited and can be used. For example, plants having a cation-exchange function include changshuohuangma, molokheiya, komatsu, duck celery, Japanese turnip, and bok choy. Regarding the part of the plant, a part of any of a leaf, a stem, and a root may be used. Among the plants, Changshuo jute and jute are preferred, and Changshuo jute which shows good results in the following examples.

In addition, Changshu Jute Zhongjia is the "Jute Jute No. 4" with the identification number 2013 of the Institute of Hemp Research, Chinese Academy of Agricultural Sciences. "Zhong Jute No. 4" has the following characteristics: Crop type: Jute.

<< Polymer agglutinating agent >> The polymer agglutinating agent is the same as the above-mentioned plant part, and is not particularly limited as long as it is a polymer agglutinating agent having the effect of removing the aforementioned inorganic wastes in the discharged water. For example, polyacrylamide (PAM), a partially hydrolyzed salt of polyacrylamide, sodium alginate, sodium polyacrylate, sodium salt of carboxymethyl cellulose (CMC, Carboxymethyl Cellulose), and the like are produced. Among these, polyacrylamide is preferably used. As the polypropylene amidamine, commercially available products such as Flopan AN 995SH, FA 920SH, FO 4490, AN 923, AN 956 (manufactured by SNF Co., Ltd.) and the like can be used.

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

<<< particles of plant powder and polymer coagulant> The mixing ratio of the plant powder particles and the polymer coagulant is preferably in a range of 10:90 to 90:10 by mass ratio. The particle surface obtained by kneading the aforementioned plant powder with the aforementioned polymer aggregating agent is preferably mixed with a coating portion of the plant powder existing on the particle surface covered with the polymer agglutinating agent, and an uncoated portion not covered by the polymer agglutinating agent. section. The median diameter of the particles is preferably 150 μm or more, more preferably 150 μm or more and 850 μm or less. When the median diameter of the particles is 150 μm or more, the sedimentation of the purification effective component is delayed, and the adsorption time of the purification effective component can be extended. Here, the median diameter (also referred to as d50) refers to the particle diameter when the particle size of the aforementioned particles is plotted, and the particle diameter is 50% of the total number in the figure (the larger particle diameter side and the particle The smaller diameter side is divided into equal size particle sizes). The median diameter can be measured by a commercially available measuring machine.

<< Other steps >> In addition to the kneading step described above, the production method of the present invention may include other steps such as a forming step, a drying step, and a pulverizing step. Specifically, the granules defined in the present invention are manufactured by a manufacturing method including the following steps: a forming step to form a shaped body obtained by forming a kneaded material obtained by the kneading step described above; and a drying step of forming the aforementioned shaped body Drying; and a pulverizing step, pulverizing the dried compact. Next, after the aforementioned pulverization step, a classification step may be included, which classifies the particles by a sieve.

In the aforementioned forming step, for example, the aforementioned kneaded material may be formed by an arbitrary forming method to form a formed body.

In the aforementioned drying step, it is preferred to use a multi-stage hot air dryer to dry the obtained compact at a temperature of 80 ° C. to 150 ° C. and conditions of 2 hours to 12 hours. It is preferable to dry the said compact, and to supply it to a crushing process. In addition, although the preferable aspect of the aforementioned drying step is the order of "drying the formed body obtained in the forming step and then pulverizing the dried formed body", it is also possible to perform "the formed body obtained in the forming step" Crushing, followed by a drying step to obtain particles ". In the aforementioned pulverizing step, a pulverizer is used, for example, an airflow type ultrafine pulverizer is used to pulverize the particles. In the aforementioned classification step, a classifier is used, and it is preferred to classify the pulverized powder using, for example, a vibratory screener or an air ratio classifier, so that the median diameter of the particles is within a desired range. Preferably, the median diameter should be in the range of 150 μm to 850 μm, so the sieve will only select particles with a particle size in the range of 150 μm to 850 μm. Powders smaller than 150 μm or more than 850 μm will be taken out and removed (screened) by the sieve.

<B; Second aspect of the water purifying agent manufacturing method> In the aforementioned water purifying agent manufacturing method, before the kneading step of kneading the plant powder and the polymer agglutinating agent, the method further includes mixing water to the polymer agglutinating agent and Step of mixing molecular agglutinating agent with water.

<< Kneading step of plant powder and polymer agglutinating agent >> The kneading step in the second aspect is specifically the same as that described in (a1) and (a2) in the first aspect, For example, including the steps defined in the following (a1) and (a2), the following two aspects (a1) and (a2) can be cited. (A1): a first kneading step, mixing water to a polymer coagulant to knead the polymer coagulant and water; and then, performing a second kneading step, mixing the plant powder to the kneaded polymer coagulant, To knead the aforementioned plant powder and polymer agglutinating agent. In the above (a1), when the plant powder and the polymer coagulant are kneaded, water may be mixed, and in this case, the following (a2) is obtained. (A2): the first kneading step, mixing water to the polymer coagulant to knead the polymer coagulant and water; and then, performing the second kneading step, mixing the plant powder and water to the kneaded polymer coagulant Agent to knead the aforementioned plant powder and polymer agglutinating agent.

As defined in the second aspect, prior to kneading with the plant powder, kneading the polymer coagulant with water in advance is effective for obtaining a kneaded system of a desired hardness. At this time, the total amount (mass) of the water added during the kneading is not particularly limited. For example, the amount of water mixed with the solid component (mass) in the water purifying agent is 1 to At 9 times, a water purifying agent that can achieve the object of the present invention can be obtained. However, as defined in the first aspect, when mixing, the total amount (mass) of water mixing is better in the range of 1.5 to 8 times than the solid content (mass) in the water purifying agent. For the requirements other than the above-mentioned requirements defined in the kneading step, the content described in the first aspect can be applied.

In the second aspect, << plant powder>, << polymer aggregating agent >>, << other additives >>, << particles of plant powder and polymer aggregating agent >>, << other steps >>, etc. 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 is to dissolve the water purifying agent obtained in the above-mentioned production method of the present invention in water, thereby obtaining a dispersion liquid containing a plant powder and a polymer coagulant, Then, the dispersion liquid is supplied to the discharged water containing the inorganic waste to remove the inorganic waste from the discharged water. Examples of the inorganic waste include inorganic waste having at least one selected from the group consisting of nickel, fluorine, iron, copper, zinc, chromium, arsenic, cadmium, and lead. In the aforementioned dispersion liquid, in addition to pure water (distilled water), water having a conductivity of 30 μS / cm or more can be used. This makes it possible to use cheaper tap water and groundwater. Even when tap water and groundwater are used in the dispersion, the concentration of inorganic ions in the discharged water can be reduced to a concentration below a desired concentration, and excellent water purification performance is exhibited. The water purification agent obtained by the manufacturing method of this invention is used, and a dispersion liquid is produced.

The discharged water treatment method of the present invention will be specifically described. For example, an alkali may be added to the discharged water to make the discharged water alkaline, so that at least a part of the heavy metal ions are not dissolved, and after the insolubilization step of forming a suspended solid, the manufacturing method of the present invention is added. The water purification agent obtained. Furthermore, the water-purifying agent obtained by the manufacturing method of this invention can also be added after polymer coagulant, such as amine, is added separately. 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 discharged water. By supplying the dispersion liquid to the discharged water, the inorganic waste is aggregated and settled, and the precipitate separated and separated can be 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 prepared as the discharge water (imaginary discharge water) used in the experiment. Next, sodium hydroxide was supplied to the above-mentioned discharged water so as to have a pH of 10, and the nickel was insolubilized by stirring. The nickel ion concentration of the supernatant liquid of the discharged water was 2 mg / L. <Water Purifying Agent> In addition, "concentrated spinach from Maebashi, Gunma Prefecture" was used as a plant, and polypropylene ammonium (PAM) was used as a polymer agglutinating agent. The granules 1 were obtained by the manufacturing method shown below, and such granules 1 were used as the water purification agent 1.

＜〈 Method of manufacturing water purification agent 〉＞ Add 5 times the mass of water to the mass of the solid content of the plant powder and the polymer aggregating agent to obtain a kneaded product (plant powder + polymer aggregating agent + water = 30kg). The kneaded product was placed in a planetary mixer (Mixer ACM-110 manufactured by Aiko Seisakusho Co., Ltd., with a capacity of 110 L), and kneaded by applying shear stress at a mixing speed of 150 rpm for 20 minutes. The obtained kneaded product is formed into a formed body. The formed article was dried using a multi-stage hot air dryer (a rack oven device manufactured by Chiyo Seisakusho Co., Ltd.) at 120 ° C for 3 hours, and then at 150 ° C for 2 hours. Next, the dried flakes were pulverized by using an air-flow type ultrafine pulverizer (Ceren Miller, manufactured by Masano Kogyo Co., Ltd.) to have a median diameter of 400 μm. The median diameter was measured with a mastersizer 2000 (manufactured by Malvern Instrument). Use a classifier (vibration sifter manufactured by Mikasa Co., Ltd.) and set it to sieved only the pulverized powder with a particle size in the range of 150 μm to 850 μm. Remove and remove (sieve out). In this way, the particles 1 are obtained and used as the water purification agent 1.

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

<Characteristic evaluation> Next, the dispersion liquid 1 containing the water-purifying agent 1 was added to the said discharged water, and the solid content was 7 mg / L, and it stirred. Here, the measurement method of "solid content" can be calculated | required by measuring the density | concentration of the mud of discharged water using a moisture meter, and inferring a solid content. The discharged water to which the dispersion liquid 1 was added was transferred to a sedimentation tank, and thereafter it was left to stand, and the state was visually confirmed every 1 hour. The time at which a clear separation of the upper clear liquid and the precipitate into two layers was confirmed was determined as the settling time. The upper clear solution was taken out and the ion concentration was measured by Lambda (Λ) 9000 (manufactured by Kyoritsu Chemical Research Institute). The following criteria were used to evaluate the water purification performance of this result. [Evaluation criteria for water purification performance] ◎: less than 1.0 mg / L (below 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 results of the dispersion viscosity 50 (mPa · sec) measured by the B-type viscosity agent. In addition, the hardness of the kneaded material obtained in the process of producing the pellets also shows the measurement results in the AR-G2 hardness measurement mode made by TA Instruments in accordance with the method described above. In addition, the above-mentioned viscosity measurement was performed using a TVC-7 type viscometer (B-type viscometer) manufactured by Toki Sangyo Co., Ltd. at a room temperature of 23 ° C using a No. 1 spindle. In Table 1-1, plant powder 1 refers to "concentrated spinach from Maebashi, Gunma Prefecture", and PAM refers to polypropylene amide (Table 1-2 to Table 1-3, and Table 2 are the same).

(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 Changshu Jute (made in China ‧ Guangzhou) and the rotation speed of the mixer in the kneading step was changed to 80 rpm. The characteristics of the water-purifying agent were evaluated in the same manner as in Example 1 using the water-purifying agent 2 composed of the particles 2. The evaluation results of Example 2 are shown in Table 1-1. 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, "Zhong Jute No. 4" which is the identification number of the Institute of Hemp Research of the Chinese Academy of Agricultural Sciences of Changshu Jute, was used. Except for this, particles 3 were produced in the same manner as in Example 2. The characteristics of the water-purifying agent were evaluated in the same manner as in Example 1 using the water-purifying agent 3 composed of the particles 3. The evaluation results of Example 3 are shown in Table 1-1. The plant powder 3 in Table 1-1 refers to "Medium Jute No. 4".

(Example 4) A granule 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. The characteristics of the water-purifying agent were evaluated in the same manner as in Example 1 using the water-purifying agent 4 composed of the particles 4. The evaluation results of Example 4 are shown in Table 1-1.

(Example 5) A granule 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. The characteristics of the water-purifying agent were evaluated in the same manner as in Example 1 using a water-purifying agent 5 made of particles 5. The evaluation results of Example 5 are shown in Table 1-1.

(Example 6) A 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. The characteristics of the water-purifying agent were evaluated in the same manner as in Example 1 using the water-purifying agent 6 composed of the particles 6. The evaluation results of Example 6 are shown in Table 1-2.

(Example 7) A 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. The characteristics of the water-purifying agent were evaluated in the same manner as in Example 1 using a water-purifying agent 7 made of particles 7. The evaluation results of Example 7 are shown in Table 1-2.

(Example 8) A pellet 8 was produced in the same manner as in Example 3, except that the water used as the dispersion liquid in Example 3 was changed to water having a conductivity of 198 μS / cm (tapuma city, Tochigi Prefecture). The characteristics of the water-purifying agent were evaluated in the same manner as in Example 1 using a water-purifying agent 8 made of particles 8. 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 used as the dispersion in Example 3 was changed to water having a conductivity of 30 μS / cm obtained by appropriately mixing tap water and distilled water in Kanuma City, Tochigi Prefecture. The characteristics of the water-purifying agent were evaluated in the same manner as in Example 1 using a water-purifying agent 9 made of particles 9. 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. The characteristics of the water-purifying agent were evaluated in the same manner as in Example 1 using a water-purifying agent 10 made of particles 10. 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 coagulant of Example 3 was changed to polyamine. The characteristics of the water-purifying agent were evaluated in the same manner as in Example 1 using the water-purifying agent 11 composed of the particles 11. 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 prepared as the discharge water (virtual discharge water) used in the experiment. Next, 8.6 mg / L of calcium chloride was added to the above-mentioned discharged water, and sodium hydroxide was added to adjust the pH to 7.5 to 9.0, and the fluorine was not dissolved while stirring. With this operation, the upper clear liquid containing micro-flock in the fluorine aqueous solution was separated from the precipitate. At this point, the ion concentration of the supernatant liquid of the discharged water was 10 mg / L. Except that the above-mentioned discharged water was used, as in Example 3, a water purification agent 3 made of particles 3 was used, and the characteristics of the water purification agent were evaluated. The evaluation results of Example 12 are shown in Tables 1-3.

(Example 13) 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 discharge water (imaginary discharge water) used in the experiment. Furthermore, while adding sodium hydroxide to the above-mentioned discharged water to a pH value of 6.5 to 9.0, the iron was not dissolved while stirring. At this point, the ion concentration of the supernatant liquid of the discharged water was 2 mg / L. Except that the above-mentioned discharged water was used, as in Example 3, a water purification agent 3 made of particles 3 was used, and the characteristics of the water purification agent were evaluated. The evaluation results of Example 13 are shown in Tables 1-3.

(Example 14) Copper sulfate pentahydrate was dissolved in pure water, and 800 g of an aqueous solution containing 100 mg / L of copper ions was prepared as the discharge water (imaginary discharge water) used in the experiment. In addition, while adding sodium hydroxide to the discharged water so that the pH value was 7.0 to 8.0, the copper was not dissolved while stirring. At this point, the ion concentration of the supernatant liquid of the discharged water was 2 mg / L. Except that the above-mentioned discharged water was used, as in Example 3, a water purification agent 3 made of particles 3 was used, and the characteristics of the water purification agent were evaluated. The evaluation results of Example 14 are shown in Tables 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 prepared as the discharge water (imaginary discharge water) used in the experiment. In addition, while adding sodium hydroxide to the discharged water to have a pH of 9.0 to 9.5, the zinc was not dissolved while stirring. At this point, the ion concentration of the supernatant liquid of the discharged water was 5 mg / L. Except that the above-mentioned discharged water was used, as in Example 3, a water purification agent 3 made of particles 3 was used, and the characteristics of the water purification agent were evaluated. The evaluation results of Example 15 are shown in Tables 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 prepared as discharge water (imaginary discharge water) used in the experiment. In addition, while adding sodium hydroxide to the discharged water to a pH value of 6.0 to 7.5, the chromium was not dissolved while stirring. At this point, the ion concentration of the supernatant liquid of the discharged water was 5 mg / L. Except that the above-mentioned discharged water was used, as in Example 3, a water purification agent 3 made of particles 3 was used, and the characteristics of the water purification agent were evaluated. The evaluation results of Example 16 are shown in Tables 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 prepared as the discharge water (virtual discharge water) used in the experiment. Next, 65 mg / L of ferric chloride and 354 mg / L of calcium chloride were added to the discharged water, and then sodium hydroxide was added to adjust the pH to 8.0 to 9.5, and arsenic was not dissolved while stirring. At this point, the ion concentration of the supernatant liquid of the discharged water was 0.05 mg / L. Except that the above-mentioned discharged water was used, as in Example 3, a water purification agent 3 made of particles 3 was used, and the characteristics of the water purification agent were evaluated. The evaluation results of Example 17 are shown in Tables 1-3. However, in Example 17, after the sedimentation time was measured in the same manner as in Example 3, the upper clear liquid was taken out, and its volume was concentrated to 1/100 by an evaporator, and the ion concentration was measured. As for the arsenic ion, if it is judged that the preferable result of the ion concentration is 0.01 mg / L or less, the result is evaluated as ◎.

[Table 1-1]

[Table 1-2]

[Table 1-3]

(Example 18) The water purification agents 3, 4 and 5 obtained in Examples 3, 4 and 5 were each replaced with the conductivity of the dispersion liquid by the same method as in Examples 3, 4 and 5. Evaluation of the characteristics of a water purifying agent in 1 μS / cm water (distilled water). Evaluation results when distilled water was used as the water of the dispersions of the water purifying agents 3, 4 and 5 and water with a conductivity of 110 μS / cm (tap water in Kanuma City, Tochigi Prefecture) were used as in Examples 3, 4 and 5 described above. The evaluation results at the time of use of the dispersion liquid are also shown in Table 2.

(Comparative Examples 1 to 2) In Example 3, Comparative Particles 1 were produced in the same manner as in Example 3, except that the amount of water added to the solid content (polymer aggregate + plant powder) was changed to 0.8 and 9 times. ~ 2. When using Comparative Water Purification Agents 1 to 2 made of Comparative Particles 1 to 2 and the same as those in Examples 3 and 18, when using water with a conductivity of 110 μS / cm (Takanuma City, Tochigi Prefecture) as the dispersion, And when using distilled water having a conductivity of 1 μS / cm as the dispersion liquid, the water purification performance of the discharged water was evaluated. The evaluation results of Comparative Examples 1 to 2 are shown in Table 2. In addition, compared with the comparative particle 1 used in Comparative Example 1, although it is also intended to measure the hardness of the mixed material obtained in the manufacturing process by the same method as in Example 1, it is because the mixed material is not sticky. It is disintegrated and has no lumps, so it cannot be measured with a hardness meter.

[Table 2]

(Example 19) Using the dispersion liquid similar to Example 3, an experiment for evaluating discharge water purification performance in Example 3 was performed 30 times. On the other hand, the water purifying agent 3 obtained in Example 3 was used instead of the dispersion liquid, and 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 amount of the water purifying agent 3 added to the discharged water was such that the solid content was 7 mg / L. The variability of the purification performance was evaluated for each experimental result. When a dispersion liquid was used, it was a result of 且, and it was confirmed that a purification result with less fluctuation can be obtained every time. On the other hand, when the water purification agent is directly injected into the discharged water, although a good result may be displayed as ◎, there are also cases where the same result is not displayed (a case where there is a result of ○ or ○ △), but because it is used Experiments are performed in the same way, so the experimental results are variable.

(Example 20) A 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. The characteristics of the water-purifying agent were evaluated in the same manner as in Example 3 using a water-purifying agent 20 made of particles 20. <Kneading step> Water of the amount shown in Table 3 below was added to the polymer coagulant, and the polymer coagulant and water were kneaded for 10 minutes. After that, the plant powder is mixed to the polymer agglutinating agent after kneading, and the plant powder and the polymer agglutinating agent are kneaded for 10 minutes. Further, the water purifying agent 20 obtained by the above method was used, and as shown in Example 18, the characteristics of the water purifying agent when the water of the dispersion liquid was changed to water (distilled water) having a conductivity of 1 μS / cm were evaluated. The evaluation result using the water purification agent 20 is shown in Table 3.

(Examples 21 to 23) Water purification agents 21 to 23 were produced in the same manner except that the water purification agent 20 was changed to the conditions shown in Table 3 below. 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 purifying agent manufactured by the manufacturing method of the present invention can be applied to a water purifying agent having a size of a drain tank for use in a large automated purification device. And it is a low cost and shows stable purification performance without change every time.

no

Claims (13)

A method for manufacturing a water purifying agent, which is a method for manufacturing a water purifying agent made of particles containing a plant powder and a polymer agglutinating agent, comprising: a kneading step, kneading a plant powder and a polymer agglutinating agent; In the aforementioned kneading step, the hardness of the kneaded material obtained through the aforementioned kneading step is to knead the plant powder and the polymer agglutination in such a manner that the stress is displayed as 3N / mm ² to 100N / mm ² under the following measurement conditions. Measurement conditions: For the aforementioned kneaded material, a stress-controlled rheometer (viscosity measuring device) was used to measure the stress at a pushing speed of 30 mm / min and a probe with a diameter of 16 mm when the pushing amount was 5 mm. The method for producing a water purifying agent according to claim 1, which conforms to any one of the following (a1), (a2), and (b): (a1): a first kneading step, Water is mixed with the polymer agglutinant to knead the polymer agglutinant and water; and then, a second kneading step is performed to mix the plant powder to the kneaded polymer agglutinant to knead the plant powder and polymer Agglutinating agent; wherein, in the first kneading step, the total amount (mass) of water mixing is 1.5 to 8 times the solid content (mass) in the water purifying agent; (a2): the first kneading step , Mixing water to the polymer agglutinating agent to knead the polymer agglutinating agent and water; and then, performing a second kneading step, mixing the plant powder and water to the kneaded polymer agglutinating agent to knead the plant Powder and polymer coagulant; wherein, in the first kneading step and the second kneading step, the total amount (mass) of water mixing with respect to the solid content (mass) in the water purifying agent; 1.5 times to 8 times; and (b): a kneading step in which the plant powder is mixed with a polymer coagulant and water to knead it; wherein, in the kneading step, compared with the solid component in the water purifying agent ( Mass), the total amount (mass) of water mixing is 1.5 to 8 times. The method for manufacturing a water purifying agent according to claim 1, comprising: a first kneading step, mixing water to the polymer agglutinating agent to knead the polymer agglutinating agent and water; and then performing a second kneading step , Mixing the plant powder to the kneaded polymer coagulant to knead the plant powder and polymer coagulant. The method for producing a water purifying agent according to claim 1, wherein the total value of the kneading time during the kneading is 15 minutes or more and 30 minutes or less 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 any one selected from the group consisting of Changshuo jute, jute, komatsu, duck celery, Japanese turnip, and seaweed. 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 Changshu jute is an identification number 2013 "Zhong jute 4" of the Institute of Hemp Research of the Chinese Academy of Agricultural Sciences. The method for producing a water purification agent according to claim 1, wherein a median diameter of the water purification agent is 150 μm or more and 850 μm or less. The method for producing a water purification agent according to claim 1, wherein the polymer agglutinating agent is polypropylene amidamide. The method for producing a water purifying agent according to claim 1, comprising: a forming step of forming a formed body having a kneaded body obtained through the aforementioned kneading step; a drying step of drying the formed body; and a pulverizing step, The dried compact was pulverized. A method for treating discharged water, which comprises dissolving a water purifying agent obtained by the method for manufacturing a water purifying agent as set forth in any one of claims 1 to 10 in water, thereby obtaining a plant powder and a polymer agglutinating agent. The dispersion liquid is then supplied to the discharged water containing the inorganic waste to remove the inorganic waste from the discharged water. The method for treating discharged water according to claim 11, wherein the discharged water is an inorganic waste having at least one 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 water in the dispersion liquid is 30 μS / cm or more.