Organic coagulant and method for producing the same, and water purification agent and method for producing the same

Abstract

To provide a water-cleaning agent which has low contents of water-insoluble components and excellent water-cleaning performance and a method for producing the same, and an organic coagulant which can be used suitably for the water-cleaning agent and a method for producing the same.SOLUTION: The invention provides, e.g., an organic coagulant which contains a plant extract, and a water-cleaning agent which contains the organic coagulant and a polymer coagulant.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an organic coagulant, a method for producing the same, a water purifying agent, and a method for producing the same.

Background Art

[0002] In recent years, in the process of manufacturing various products in factories and the like, a large amount of waste liquid containing environmental load substances such as metal ions and fluoride ions as inorganic ions has been generated, and water purification treatment using a water purifying agent has been performed.

[0003] So far, as a water purifying agent that makes use of the charge-neutralizing role of plants, a water purifying agent composed of granules containing a mixture of plant powder and a polymer flocculant has been proposed (see, for example, Patent Document 1). The proposed technology is a very useful technology that is excellent in water purification performance and can also be suitably used for an automatic purification device for drainage water.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] As described above, the technology described in Patent Document 1 is a very useful technology. On the other hand, since plants contain components that are insoluble in water, when used as a flocculant, it is necessary to set the viscosity at the time of dissolution to a relatively high state in order to prevent the components insoluble in the water from settling. Therefore, only high-viscosity materials could be used, or the range of product characteristics such as the composition ratio of each component in the water purifying agent was limited. Also, when the viscosity is not sufficient (low), there is a possibility that the components insoluble in the water that have precipitated may clog pipes and the like. Therefore, there is a strong demand for the prompt development of a water purifying agent with a low content of components insoluble in water.

[0006] The present invention aims to solve the aforementioned problems in the conventional approach and achieve the following objectives. Specifically, the present invention aims to provide a water purification agent with a low content of water-insoluble components and excellent water purification performance, a method for producing the same, and an organic coagulant that can be suitably used with the water purification agent, and a method for producing the same. [Means for solving the problem]

[0007] As a result of diligent research, the inventors have discovered that by including plant extracts, it is possible to remove water-insoluble components contained in plants while still achieving excellent water purification properties. Furthermore, because it is possible to remove components that settle when dissolved in water, it is possible to create a low-viscosity material, which significantly improves the design flexibility of water purification agents in terms of viscosity and mixing ratio.

[0008] The means to solve the aforementioned problem are as follows: <1> This is an organic coagulant characterized by containing plant extracts. <2> The conductivity of the organic coagulant is 12 to 350 mS / m when the solid content is 0.1% by mass. <1> It is an organic coagulant as described above. <3> The zeta potential is anionic. <1> from <2> It is an organic coagulant as described in any of the following. <4> The plant extract contains water-soluble natural lignocellulose. <1> from <3> It is an organic coagulant as described in any of the following. <5> The plant of the plant extract is at least one selected from the group consisting of straw, reeds, and hemp. <1> from <4> It is an organic coagulant as described in any of the following. <6> The aforementioned <1> from <5> A method for producing an organic coagulant as described in any of the following: The grinding process for crushing plants, An extraction process in which crushed plants and water are mixed to obtain a plant extract, A filtration step of filtering the plant extract to obtain a liquid component, This is a method for producing an organic coagulant, characterized by containing the following: <7> The extraction process is carried out under any of the following conditions: room temperature, heating, or heating and pressurizing. <6> This is a method for producing the organic coagulant described above. <8> The aforementioned <1> from <5> An organic coagulant as described in any of the following, This water purification agent is characterized by containing a polymer flocculant. <9> The particle <8> This is the water purification agent described in [the document / article]. <10> The mass ratio (organic coagulant / polymer flocculant) of the organic coagulant to the polymer flocculant is 0.01 / 99.99 to 99.99 / 0.01. <8> from <9> It is a water purification agent described in any of the following. <11> The water purification agent contains 5% by mass or less of insoluble components in water. <8> from <10> It is a water purification agent described in any of the following. <12> The aforementioned <1> from <5> A method for producing a water purification agent containing an organic coagulant and a polymer flocculant as described in any of the following: The polymer flocculant and the <1> from <5> A kneading step to obtain a kneaded product by kneading with an organic coagulant described in any of the above, A drying step in which the kneaded material is dried to obtain a dried product, A grinding step to obtain a pulverized product by grinding the aforementioned dried material, A classification step to obtain a water purification agent by classifying the aforementioned pulverized material, This is a method for producing a water purification agent characterized by containing [a specific ingredient]. [Effects of the Invention]

[0009] According to the present invention, it is possible to solve the aforementioned problems in the conventional method and achieve the aforementioned objectives, and to provide a water purification agent and a method for producing the same that have a low content of water-insoluble components and excellent water purification performance, as well as an organic coagulant that can be suitably used in the water purification agent and a method for producing the same. [Brief explanation of the drawing]

[0010] [Figure 1]Figure 1 is a graph showing the results of measuring the turbidity of Test Examples 1 to 5. [Figure 2] Figure 2 is a photograph of the state when measuring the turbidity of Test Examples 1 to 5.

Mode for Carrying Out the Invention

[0011] (Organic Flocculant) The organic flocculant of the present invention contains at least a plant extract and, if necessary, further contains other components.

[0012] <Plant Extract> The plant of the plant extract is not particularly limited and can be appropriately selected according to the purpose. The plants may be used alone or in combination of two or more. Among the plants, at least one selected from the group consisting of straw, reed, and hemp is preferable. The hemp is not particularly limited and can be appropriately selected according to the purpose, but Changshuohuangma is preferably mentioned.

[0013] As the Changshuohuangma, Changshuohuangma produced in Changsha City, China, or "Zhonghuangma No. 4" with the identification number of Guojianma 2013 by the Institute of Bast Fiber Crops, Chinese Academy of Agricultural Sciences, "Zhonghuangma No. 3" with the identification number of Wanpin Jian Dengzi No. 1209006, "Zhonghuangma No. 1" with the identification number of XPD005-2005, or "Zhonghongma" with the identification number of Wanpin Jian Dengzi No. 1209001, etc. can be preferably used. Among these, the "Zhonghuangma No. 4", the "Zhonghuangma No. 3", and the "Zhonghongma" are more preferable, and the "Zhonghuangma No. 4" is particularly preferable.

[0014] The "Zhonghuangma No. 4" has the following characteristics. Agricultural product type: Jute Origin of variety: Propagated from the crossbred F1 generation of Xianghuangma No. 3 × 0-4(l) and Xianghuangma No. 3 Characteristic features: Zhonghuangma No. 4 is a normal variety of jute of the long fruit type, with a green stem, a cylindrical stem, needle-shaped leaves with scattered leaf blades, a green leaf stalk, a small angle with the main stem, and lateral buds and stipules. The calyx is green, long fruit cylindrical, five-chambered, and the seeds are of a late-maturing variety.

[0015] The plant extract preferably contains water-soluble natural lignocellulose.

[0016] -Water-soluble natural lignocellulose- The water-soluble natural lignocellulose (hereinafter sometimes referred to as "lignocellulose") is composed of cellulose, hemicellulose, and lignin. The lignin is a main component that constitutes the plant cell wall together with polysaccharides (cellulose, hemicellulose). There is no particular limitation on the content of the lignocellulose in the plant extract, and it can be appropriately selected according to the purpose.

[0017] There is no particular limitation on the method for preparing the plant extract, and a known method for preparing a plant extract can be appropriately selected according to the purpose. However, it is preferably prepared by the extraction step in the method for producing the organic flocculant of the present invention described later.

[0018] There is no particular limitation on the content of the plant extract in the organic flocculant, and it can be appropriately selected according to the purpose.

[0019] <Other components> There is no particular limitation on the other components in the organic flocculant as long as the effects of the present invention are not impaired, and they can be appropriately selected according to the purpose. <F There is no particular limitation on the content of the other components in the organic flocculant, and it can be appropriately selected according to the purpose.

[0020] There is no particular limitation on the form of the organic flocculant, and it can be appropriately selected according to the purpose. It may be liquid or solid. The organic flocculant can be produced as a liquid component as described later, but the liquid component can also be solidified and dissolved in water at the time of use.

[0021] <Viscosity> There are no particular restrictions on the viscosity of the organic coagulant, and it can be appropriately selected depending on the purpose. However, when it is an aqueous solution with a solid content of 0.1% by mass, the viscosity is typically 0.5 to 5 mPa·s. The viscosity can be measured using a Toki Sangyo TVC-10 viscometer (Type B viscometer) at 23°C with a No. 0 rotor.

[0022] <Conductivity> There are no particular restrictions on the conductivity of the organic coagulant, and it can be appropriately selected depending on the purpose. However, when it is an aqueous solution with a solid content of 0.1% by mass, the conductivity is preferably 12 to 350 mS / m, and more preferably 50 to 350 mS / m. The aforementioned conductivity can be measured at a liquid temperature of 22°C using a conductivity meter: benchtop type F-70 (manufactured by Horiba, Ltd.).

[0023] <Zeta potential> There are no particular restrictions on the zeta potential of the organic coagulant, and it can be appropriately selected depending on the purpose, but it is preferable that it be anionic.

[0024] Furthermore, the Δzeta potential of the organic coagulant is preferably 40 mV or higher, more preferably 45 mV, and particularly preferably 50 mV or higher, as measured and calculated as described below. [measurement] Take 600 mL of potassium fluoride aqueous solution, adjusted to a concentration of 500 ppm, into a beaker and add 3.5 mL of 35% by mass calcium fluoride aqueous solution while stirring well. Next, add 5% by mass sulfuric acid while stirring well, and adjust the pH to 4.5 ± 0.25. The zeta potential (hereinafter sometimes referred to as "CaF2 zeta potential") of the solution whose pH has been adjusted as described above is measured. Furthermore, 100 mL of the pH-adjusted solution is taken, and while stirring at 500 rpm, the organic coagulant is added to it to a concentration of 1% by mass. After stopping the stirring, the supernatant is sampled and the zeta potential (hereinafter sometimes referred to as "zeta potential after addition of organic coagulant") is measured. The difference between the CaF2 zeta potential (A) and the zeta potential after the addition of the organic coagulant (B) is calculated as the Δzeta potential. The zeta potential can be measured by dynamic scattering.

[0025] The aforementioned organic coagulant can be suitably produced by the method for producing the organic coagulant of the present invention, as described later.

[0026] As shown in the examples below, the aforementioned organic coagulant has an excellent flocculation effect and can therefore be used in water purification treatment in combination with polymer flocculants. Furthermore, the water purification treatment can be carried out without using inorganic flocculants such as aluminum-based inorganic flocculants, iron-based inorganic flocculants, or slaked lime. The aforementioned organic coagulant can also be suitably used in the water purification agent of the present invention, which will be described later.

[0027] (Method of manufacturing organic coagulants) The method for producing the organic coagulant of the present invention is the method for producing the organic coagulant of the present invention described above, comprising at least a grinding step, an extraction step, and a filtration step, and optionally including other steps.

[0028] <Grinding process> The aforementioned crushing process is a process of crushing plants.

[0029] There are no particular restrictions on the parts of the plant (hereinafter sometimes referred to as "extracted raw materials") used, and they can be appropriately selected according to the purpose. Examples include leaves, stems, and bark. These may be used individually or in combination of two or more.

[0030] The aforementioned extraction material may be a dried or undried product, but a dried product is preferred.

[0031] There are no particular restrictions on the method for crushing the aforementioned plants, and any known method can be appropriately selected. There are no particular restrictions on the degree of grinding, and it can be appropriately selected according to the purpose.

[0032] <Extraction process> The extraction process involves mixing pulverized plants with water to obtain a plant extract. The extraction process may be performed once or two or more times. The extraction step only requires at least one extraction using water as the extraction solvent, and may be combined with extraction using an organic solvent such as ethyl acetate, but extraction with water alone is preferred.

[0033] There are no particular restrictions on the type of water mentioned above; it can be selected appropriately depending on the purpose, for example, pure water.

[0034] In the extraction step, the pulverized plants may be added to the extraction solvent, or the extraction solvent may be added to the pulverized plants. Furthermore, stirring may be performed in the extraction step as needed.

[0035] There are no particular restrictions on the concentration of the raw material to be extracted during the extraction process, and it can be appropriately selected according to the purpose. For example, 1 to 10% by mass is one possible range.

[0036] There are no particular restrictions on the temperature and pressure used in the extraction process; they can be appropriately selected depending on the purpose. Examples include room temperature, heating, and heating and pressurizing. The aforementioned room temperature refers to a temperature of approximately 20-28°C. The aforementioned heating refers to raising the temperature to a level higher than room temperature. The aforementioned heating and pressurizing refers to a temperature higher than room temperature and a pressure higher than atmospheric pressure. For example, a pressure higher than atmospheric pressure can be approximately 2 atm.

[0037] There are no particular restrictions on the extraction time, and it can be appropriately selected depending on the purpose, for example, from 10 minutes to 24 hours.

[0038] There are no particular restrictions on the method for determining whether or not lignocellulose is present in the plant extract; known methods can be appropriately selected. For example, it can be determined from the decomposition products detected by thermal decomposition GC-MS.

[0039] <Filtration process> The filtration step involves filtering the plant extract to obtain a liquid component (hereinafter sometimes referred to as "filtrate"). By performing the aforementioned filtration, a plant extract free from water-insoluble components can be obtained.

[0040] There are no particular restrictions on the filtration method, and any known method can be appropriately selected.

[0041] There are no particular restrictions on the amount of solids in the liquid component, and it can be appropriately selected depending on the purpose. For example, it can be 0.05 to 2% by mass. There are no particular restrictions on the method for measuring the solid content, and it can be appropriately selected depending on the purpose. For example, the filtrate can be dried and the amount of solidified material obtained can be used to calculate the solid content.

[0042] <Other processes> The aforementioned other steps are not particularly limited as long as they do not impair the effects of the present invention, and can be appropriately selected depending on the purpose.

[0043] (Water purifier) The water purification agent of the present invention comprises at least the organic coagulant of the present invention and a polymer flocculant, and optionally further comprises other components.

[0044] <Organic coagulant> The organic coagulant used is the organic coagulant of the present invention described above. There are no particular restrictions on the amount of the organic coagulant in the water purification agent, and it can be appropriately selected depending on the purpose. By adjusting the amount of the organic coagulant, the amount of plant extract in the water purification agent can be adjusted.

[0045] <Polymer flocculant> The polymer flocculant is not particularly limited as long as it exhibits the effect of removing the inorganic unwanted substances in wastewater, and can be appropriately selected according to the purpose. Examples include polymers containing acrylamide (sometimes simply referred to as "polyacrylamide" or "PAM"), polyamines, sodium alginate, sodium polyacrylate, and sodium carboxymethylcellulose (CMC) salt. Among these, polymers containing acrylamide, polyacrylamide, and sodium polyacrylate are preferred. The polymer flocculant may have an ionic structure. When the ion is a cation, examples include ammonium salts and sulfonium salts. When the ion is anion, examples include carboxylate salts. The aforementioned polymer flocculant may be used alone or in combination of two or more types. There are no particular restrictions on the content of the polymer flocculant in the water purification agent, and it can be appropriately selected depending on the purpose.

[0046] As the polyacrylamide, commercially available products can be used. Examples of such commercially available products include Flopam AN 905, Flopam AN 926, and Flopam AN 956 (all manufactured by SNF Co., Ltd.); and Akofloc A-100 and Akofloc A-150 (both manufactured by MT Aquapolymer Co., Ltd.). As sodium polyacrylate, commercially available products can be used, and examples of such commercially available products include Akofloc A-190 (manufactured by MT Aquapolymer Co., Ltd.) and PA-331 (manufactured by Kurita Water Industries Ltd.).

[0047] There are no particular restrictions on the mass ratio (organic coagulant / polymer flocculant) of the organic coagulant to the polymer flocculant, and it can be appropriately selected depending on the purpose, but 0.01 / 99.99 to 99.99 / 0.01 is preferred. Within this preferred range, excellent water purification performance with sufficient microfloc adsorption effect is exhibited. In this invention, the mass ratio of the organic coagulant to the polymer flocculant is calculated based on the dry mass of each component.

[0048] <Other ingredients> Other components in the water purification agent are not particularly limited as long as they do not impair the effects of the present invention, and can be appropriately selected depending on the purpose. Examples include preservatives, fillers, thickeners, colorants, thixotropic agents, and other additives. These may be used individually or in combination of two or more. There are no particular restrictions on the amount of the aforementioned other components in the water purification agent, and they can be appropriately selected depending on the purpose.

[0049] There are no particular restrictions on the shape of the water purification agent, and it can be appropriately selected depending on the purpose, but particles (hereinafter sometimes referred to as "granules" or "granulated material") are preferred.

[0050] There are no particular restrictions on the content of water-insoluble components in the water purification agent, and it can be appropriately selected depending on the purpose, but it is preferably 5% by mass or less, and it is more preferable that it does not contain water-insoluble components. The aforementioned water-insoluble components refer to components that do not dissolve in pure water at 25°C under the condition of stirring at 500 rpm for 30 minutes. There are no particular restrictions on the method for calculating the content of the insoluble components in water, and a suitable method can be selected depending on the purpose. For example, the solution can be centrifuged at a centrifugal force of 2,500 G for 5 minutes, the supernatant can be removed, the weight of the dried residue can be measured, and the content of the insoluble components in water in the water purification agent can be calculated from that value.

[0051] There are no particular restrictions on the method for producing the water purification agent, and it can be appropriately selected depending on the purpose, but it is preferable to produce it using the method for producing the water purification agent of the present invention, which will be described later.

[0052] As shown in the examples below, the aforementioned water purification agent has excellent water purification properties while reducing water-insoluble components contained in plants. Therefore, it can be made from low-viscosity materials, greatly increasing the design flexibility of the water purification agent, such as viscosity and mixing ratio.

[0053] (Method of manufacturing water purification agent) The present invention relates to a method for producing a water purification agent containing the organic coagulant and polymer flocculant of the present invention, comprising at least a kneading step, a drying step, a grinding step, and a classification step, and optionally including other steps such as a molding step.

[0054] <Mixing process> The aforementioned kneading step is a step of kneading the polymer flocculant and the organic coagulant of the present invention to obtain a kneaded product. There are no particular restrictions on the kneading method, and it can be appropriately selected depending on the purpose. For example, one method is to add a liquid organic coagulant to the polymer flocculant and knead it. Water may be added in the kneading step as needed. Mixing is performed using a mixer, such as a vertical mixer like a planetary mixer, with the rotation speed and time set within a predetermined range. The rotation speed and time during mixing in the mixer can be appropriately set while considering conditions such as the mixing ratio of the organic coagulant and the polymer flocculant. For example, the rotation speed is preferably 20 rpm to 150 rpm, and the time is preferably 5 minutes to 25 minutes.

[0055] <Drying process> The drying step is a step of drying the kneaded material to obtain a dried product.

[0056] A molding step (sometimes referred to as a "stretching and sheeting step") may be included between the kneading step and the drying step to obtain a molded product in which the kneaded material is formed into a sheet. In the molding process, the resulting kneaded material is stretched using a roller to a thickness of 2 mm to 30 mm, preferably to about 10 mm, and then formed into a sheet.

[0057] In the drying process, the kneaded material or the molded product may be dried using a multi-stage hot air dryer at a temperature of 80°C to 150°C for 2 to 12 hours.

[0058] <Grinding process> The aforementioned grinding step is a step of grinding the dried material to obtain a pulverized material.

[0059] In the aforementioned grinding process, it is preferable to use a grinder, such as an air-flow type ultrafine grinder, to grind the material so that the median diameter is in the range of 150 μm to 900 μm.

[0060] <Classification process> The classification process is a process of classifying the pulverized material to obtain a water purification agent. In the aforementioned classification process, the pulverized powder is preferably classified using a classifier, such as a vibrating sieve or a cartridge-type sieve, to separate the granulated material so that the median diameter is in the range of 150 μm to 900 μm, with the particle size being within a predetermined range.

[0061] <Other processes> The aforementioned other steps are not particularly limited as long as they do not impair the effects of the present invention, and can be appropriately selected depending on the purpose. Examples include the molding step described above.

[0062] The above manufacturing method allows for the production of granular water purification agents.

[0063] (Water purification methods) The present invention also relates to a water purification method using the water purification agent of the present invention. The water purification method involves dissolving the water purification agent in water to obtain a dispersion of an organic coagulant and a polymer flocculant, and then applying the dispersion to the wastewater to remove inorganic waste.

[0064] Examples of the aforementioned inorganic waste include nickel, fluorine, iron, copper, zinc, chromium, arsenic, cadmium, tin, and lead. These may be present individually or in combination of two or more elements.

[0065] The aforementioned water purification method will now be explained in detail. In the wastewater, inorganic ions such as nickel ions, fluoride ions, iron ions, copper ions, zinc ions, chromium ions, arsenic ions, cadmium ions, tin ions, and lead ions in the inorganic waste are subjected to an immobilization treatment by adding an inorganic coagulant to form microflocs. The aforementioned dispersion, prepared as an aqueous solution of 0.05% to 0.2% by mass, is then supplied to this wastewater. The microflocs are then allowed to coagulate and settle, and the settled precipitate is removed, thereby purifying the wastewater. In the aforementioned insolubilization treatment, it is preferable, for example, to add a base to the wastewater to make it alkaline, and then add an inorganic coagulant to insolubilize the inorganic ions. Examples of inorganic flocculants include ferric chloride, polyferric sulfate, ferrous sulfate, aluminum sulfate, polyaluminum chloride (PAC), and slaked lime. These may be used individually or in combination of two or more. [Examples]

[0066] The following describes examples of the present invention, but the present invention is not limited in any way to these examples.

[0067] (Example 1: Organic Coagulant 1) <Manufacturing of Organic Coagulant 1> The raw material for extraction was dried leaves of "Zhonghuangma No. 4," a variety of hemp with identification number 2013 by the Institute of Hemp, Chinese Academy of Agricultural Sciences. Pure water was used as the extraction solvent, and the extraction was carried out as described below. The aforementioned raw materials were dried in the sun until their moisture content was 5% by mass or less, then pulverized using an atomizer (hammer mill, manufactured by Masuko Sangyo Co., Ltd.), and only particles with a diameter in the range of 100 μm to 400 μm were used.

[0068] -extraction- The extraction raw materials were added to the aforementioned pure water to a concentration of 4% by mass, stirred, and extracted under the extraction conditions described below. The filtrate was then filtered to remove insoluble components (solid content: 1.3% by mass). The solid content was calculated from the amount of solidified material obtained by drying the filtrate in an oven. [Extraction conditions] · Temperature ··· 25℃ • Duration • 60 minutes • Pressure • Atmospheric pressure (no pressure manipulation)

[0069] The filtrate was diluted with pure water to a solid content of 0.1% by mass to obtain organic coagulant 1.

[0070] <Rating> -viscosity- The viscosity of the aforementioned organic coagulant 1 was measured using a Toki Sangyo TVC-10 viscometer (Type B viscometer) at 23°C with rotor No. 0.

[0071] -conductivity- The conductivity of the organic coagulant 1 was measured at a liquid temperature of 22°C using a conductivity meter: benchtop type F-70 (manufactured by Horiba, Ltd.).

[0072] -Zeta potential- 600 mL of potassium fluoride aqueous solution, adjusted to a potassium fluoride concentration of 500 ppm, was placed in a beaker, and 3.5 mL of 35% by mass calcium fluoride aqueous solution was added while stirring well. Next, 5% by mass sulfuric acid was added while stirring well, and the pH was adjusted to 4.5 ± 0.25. The zeta potential (hereinafter sometimes referred to as "CaF2 zeta potential") of the pH-adjusted solution described above was measured using a zetasizing nano ZSP (manufactured by Malvern Panalytical). Furthermore, 100 mL of the pH-adjusted solution described above was taken, and while stirring at 500 rpm, the organic coagulant 1 was added to achieve a concentration of 1% by mass. After stopping the stirring, the supernatant was sampled, and the zeta potential (hereinafter sometimes referred to as "zeta potential after addition of organic coagulant") was measured in the same manner as described above. The difference between the CaF2 zeta potential (A) and the zeta potential after the addition of the organic coagulant (B) was calculated as the Δzeta potential, and the coagulation performance due to charge neutralization was evaluated.

[0073] -Water purification treatment- 600 mL of fluorinated raw water (fluorine concentration 500 mg / L) was used as the wastewater to be treated. Next, 3.5 mL of 35% by mass CaCl2 and 100 mg / L of the organic coagulant 1 were added to the wastewater, and the mixture was stirred while adding 5% by mass NaOH (to adjust the pH to 7.5). This operation separated the wastewater into a supernatant containing microflocs and a precipitate. Next, 2 mg / L of anionic polymer flocculant (Clifloc PA-331 (manufactured by Kurita Water Industries Ltd.)) was added to the wastewater consisting of the supernatant liquid containing the above-mentioned microflocs and the precipitate, and after stirring was maintained for 1 minute, the "fluorine (F) concentration" was measured as follows.

[0074] --Measuring fluoride concentration-- The supernatant was sampled 2 minutes after stirring was stopped, and the fluorine concentration was measured using a digital water analyzer, the Digital Pack Test (manufactured by Kyoritsu Chemical Research Institute Co., Ltd.), which uses the lanthanum-alizarin complexone spectrophotometric method.

[0075] (Example 2: Organic Coagulant 2) <Manufacturing of Organic Coagulant 2> A filtrate (solid content: 1.6% by mass) was obtained in the same manner as in Example 1, except that the extraction conditions in the <production of organic coagulant 1> of Example 1 were as follows. [Extraction conditions] · Temperature ··· 70℃ • Duration • 60 minutes • Pressure • Atmospheric pressure (no pressure manipulation) Next, the filtrate was diluted with pure water to a solid content of 0.1% by mass to obtain organic coagulant 2.

[0076] <Rating> Viscosity, conductivity, zeta potential, and water purification treatment were evaluated in the same manner as in the evaluation of Example 1 described above.

[0077] (Example 3: Organic Coagulant 3) <Manufacturing of Organic Coagulant 3> A filtrate (solid content: 3.5% by mass) was obtained in the same manner as in Example 1, except that the extraction conditions in the <production of organic coagulant 1> of Example 1 were as follows. [Extraction conditions] · Temperature ··· 100℃ • Duration • 60 minutes • Pressure • Atmospheric pressure (no pressure manipulation) Next, the filtrate was diluted with pure water to a solid content of 0.1% by mass to obtain organic coagulant 3.

[0078] <Rating> Viscosity, conductivity, zeta potential, and water purification treatment were evaluated in the same manner as in the evaluation of Example 1 described above.

[0079] (Example 4: Organic Coagulant 4) <Manufacturing of Organic Coagulant 4> A filtrate (solid content: 4.5% by mass) was obtained in the same manner as in Example 1, except that the extraction conditions in the <production of organic coagulant 1> of Example 1 were as follows. [Extraction conditions] · Temperature ··· 130℃ • Duration • 60 minutes • Pressure ··· 2 atm Next, the filtrate was diluted with pure water to a solid content of 0.1% by mass to obtain organic coagulant 4.

[0080] <Rating> Viscosity, conductivity, zeta potential, and water purification treatment were evaluated in the same manner as in the evaluation of Example 1 described above.

[0081] (Example 5: Organic Coagulant 5) <Manufacturing of Organic Coagulant 5> A filtrate (solid content: 0.06% by mass) was obtained in the same manner as in Example 1, except that the extraction raw materials and extraction conditions in Example 1 were as follows. [Extraction raw material] This product consists of dried parts (stem, bark, and leaves) of "Zhong Huang Ma No. 4," a variety of hemp with identification number 2013, certified by the Institute of Hemp, Chinese Academy of Agricultural Sciences. The extracted raw material was sun-dried until the moisture content was 5% by mass or less, then pulverized using an atomizer (hammer mill, manufactured by Masuko Sangyo Co., Ltd.), and only particles with a diameter in the range of 100 μm to 400 μm were used. [Extraction conditions] · Temperature ··· 25℃ • Duration • 60 minutes • Pressure • Atmospheric pressure (no pressure manipulation) Next, the filtrate was concentrated under reduced pressure to obtain organic coagulant 5, with a solid content of 0.1% by mass.

[0082] <Rating> Viscosity, conductivity, zeta potential, and water purification treatment were evaluated in the same manner as in the evaluation of Example 1 described above.

[0083] (Example 6: Organic Coagulant 6) <Manufacturing of Organic Coagulant 6> The raw material used for extraction was dried leaves of "Zhonghuangma No. 4," a variety of hemp with identification number 2013 from the Institute of Hemp Species, Chinese Academy of Agricultural Sciences, and the extraction was carried out as follows. The aforementioned raw materials were dried in the sun until their moisture content was 5% by mass or less, then pulverized using an atomizer (hammer mill, manufactured by Masuko Sangyo Co., Ltd.), and only particles with a diameter in the range of 100 μm to 400 μm were used.

[0084] -extraction- Ethyl acetate was added to the aforementioned raw material to make a 10% by mass solution, which was allowed to stand at room temperature (23°C) for 8 hours and then filtered. The residue was washed with ethyl acetate. Subsequently, the residue was further extracted with pure water (temperature: 25°C, time: 60 minutes, pressure: atmospheric pressure (no pressure manipulation)) to obtain the supernatant, and components with a molecular weight cutoff of 12,000 or more were separated from the supernatant by dialysis. The separated solution was concentrated under reduced pressure so that the solid content was 0.1% by mass, and this was obtained as organic coagulant 6.

[0085] <Rating> Viscosity, conductivity, zeta potential, and water purification treatment were evaluated in the same manner as in the evaluation of Example 1 described above.

[0086] (Example 7: Organic Coagulant 7) <Manufacturing of Organic Coagulant 7> In the dialysis operation described in Example 6, the component with a molecular weight cutoff of less than 12,000 obtained by the dialysis operation was further dialyzed to obtain a component with a molecular weight cutoff of less than 6,000, and the component with a molecular weight cutoff of less than 6,000 was further dialyzed to separate the component with a molecular weight cutoff of less than 3,000. The separated solution was concentrated under reduced pressure to obtain organic coagulant 7, with a solid content of 0.1% by mass.

[0087] <Rating> Viscosity, conductivity, zeta potential, and water purification treatment were evaluated in the same manner as in the evaluation of Example 1 described above.

[0088] (Comparative Example 1: Inorganic Flocculant) <Rating> -Water purification treatment- In the water purification treatment of Example 1, the addition of 100 mg / L of organic coagulant 1 was replaced with 32 mg / L of 8% by mass Al2(SO4)3·16H2O. Otherwise, the water purification treatment was carried out in the same manner as in Example 1.

[0089] (Comparative Example 2: Without organic and inorganic coagulants) <Rating> -Water purification treatment- The water purification treatment was carried out in the same manner as in Example 1, except that the organic coagulant 1 was not used in the water purification treatment of Example 1.

[0090] (Comparative Example 3: Comparative Coagulant 1) <Manufacturing of Comparative Coagulant 1> Dried rice husks were used as the extraction material, and pure water was used as the extraction solvent. The extraction was carried out as described below. The aforementioned raw materials were dried in the sun until their moisture content was 5% by mass or less, then pulverized using an atomizer (hammer mill, manufactured by Masuko Sangyo Co., Ltd.), and only particles with a diameter in the range of 100 μm to 400 μm were used.

[0091] -extraction- The extraction raw material was added to the pure water to a concentration of 4% by mass, stirred, and extracted under the extraction conditions described below. After extraction, the filtrate (solid content: 0.005% by mass) was filtered to remove insoluble components. [Extraction conditions] · Temperature ··· 95℃ • Duration • 60 minutes • Pressure • Atmospheric pressure (no pressure manipulation) Next, the filtrate was concentrated under reduced pressure to a solid content of 0.1% by mass, and this was used as comparative coagulant 1.

[0092] <Rating> Viscosity, conductivity, zeta potential, and water purification treatment were evaluated in the same manner as in the evaluation of Example 1 described above.

[0093] (Comparative Example 4: Comparative Coagulant 2) <Manufacturing of Comparative Coagulant 2> A filtrate (solid content: 0.015% by mass) was obtained in the same manner as in Comparative Example 3, except that the extraction conditions in the <Production of Comparative Coagulant 1> of Comparative Example 3 were as follows. [Extraction conditions] · Temperature ··· 130℃ • Duration • 60 minutes • Pressure ··· 2 atm Next, the filtrate was concentrated under reduced pressure to a solid content of 0.1% by mass, and this was used as comparative coagulant 2.

[0094] <Rating> Viscosity, conductivity, zeta potential, and water purification treatment were evaluated in the same manner as in the evaluation of Example 1 described above.

[0095] The results of Examples 1-7 and Comparative Examples 1-4 described above are shown in Tables 1 and 2 below.

[0096] [Table 1] In Table 1, the "*" indicates the reference to paragraph

[0084] .

[0097] [Table 2]

[0098] As shown in Tables 1 and 2, it was confirmed that when the organic coagulant of the present invention was used, the fluorine concentration in the supernatant after water purification treatment was reduced.

[0099] (Test Example 1: Water Purifier 1) <Manufacturing of water purification agent 1> Using the organic coagulant 5 of Example 5, a granular water purification agent 1 was produced as described below. A mixture (polymer flocculant + organic coagulant = 30 kg) obtained by adding 5% by mass of the organic coagulant 5 to a polymer flocculant (AN926VHM (manufactured by SNF Co., Ltd.)) was placed in a planetary mixer (ACM-110 mixer, capacity 110 L, manufactured by Aikousha Seisakusho Co., Ltd.) and kneaded under shear at a rotation speed of 150 rpm for 20 minutes. The resulting mixture was stretched using a roller in a press machine (Komatsu Industries Co., Ltd., 45t press machine) to produce a sheet-like molded product with a thickness of approximately 10 mm. This molded product was dried using a multi-stage hot air dryer (manufactured by Nanayo Seisakusho Co., Ltd., rack-type oven device) at 120°C for 3 hours, and then at 150°C for 2 hours. Next, the dried sheets were pulverized using an air-flow type ultrafine pulverizer (Selenium Mirror, manufactured by Masuko Sangyo Co., Ltd.) to a median diameter of 400 μm. The median diameter was measured using a Mastersizer 2000 (Malvern Instruments). The pulverized powder was sorted using a classifier (Dalton Co., Ltd., vibrating sieve machine) to select only particles with a diameter between 200 μm and 900 μm. Particles smaller than 200 μm and larger than 900 μm were sieved and removed. In this manner, granules were obtained and designated as water purification agent 1. The content of water-insoluble components in water in water purification agent 1 was 5% by mass or less.

[0100] <Rating> -Turbidity- As the test wastewater, 500 mL of a solution containing dispersed kaolinite (kaolinite concentration 50 ppm) was used. Next, 0.07 mL of 10% by mass polyaluminum chloride (PAC) was added to the wastewater, and the pH was adjusted to 7-8 with 0.21 mL of 5% by mass sodium hydroxide. Subsequently, 1.5 mL of an aqueous solution containing 0.1% by mass of the water purification agent 1 was added, and the turbidity of the supernatant was measured within 10 seconds after addition. The measurement was performed in accordance with JIS K 0101:1998 (Test methods for industrial water 9.2 Transmitted light turbidity), using a HACH DR 3900 spectrophotometer.

[0101] (Test example 2: Water purification agent 2) <Manufacturing of Water Purifier 2> Water purification agent 2 was manufactured in the same manner as in Test Example 1, except that the mixture of polymer flocculant and organic coagulant 5 in Test Example 1 was replaced with a mixture obtained by adding three times the mass of water relative to the combined mass of the extracted raw material (plant powder) used in the production of the organic coagulant 5 and the polymer flocculant (AN926VHM (manufactured by SNF Co., Ltd.)) (plant powder + polymer flocculant + water = 30 kg). The content of insoluble components in water in water in water purification agent 2 was 20% by mass.

[0102] <Rating> Turbidity was measured in the same manner as in Test Example 1 described above.

[0103] (Test example 3: Water purification agent 3) <Manufacturing of water purification agent 3> Water purification agent 3 was manufactured in the same manner as in Test Example 2, except that plant powder was not used. Water purification agent 3 does not contain any water-insoluble components.

[0104] <Rating> Turbidity was measured in the same manner as in Test Example 1 described above.

[0105] (Test example 4: Water purification agent 4) <Manufacturing of water purification agent 4> A water purification agent 4 was manufactured in the same manner as in Test Example 1, except that the organic coagulant 5 in Test Example 1 was replaced with the organic coagulant 6 in Example 6. The content of water-insoluble components in the water purification agent 4 was 5% by mass or less.

[0106] <Rating> Turbidity was measured in the same manner as in Test Example 1 described above.

[0107] (Test example 5: Water purification agent 5) <Manufacturing of water purification agent 5> A water purification agent 5 was manufactured in the same manner as in Test Example 1, except that the organic coagulant 5 in Test Example 1 was replaced with the organic coagulant 7 in Example 7. The content of water-insoluble components in the water purification agent 5 was 5% by mass or less.

[0108] <Rating> Turbidity was measured in the same manner as in Test Example 1 described above.

[0109] The results of the above-described test examples 1 to 5 are shown in Figures 1 and 2. Figure 1 is a graph showing the results of the turbidity measurement, and Figure 2 is a photograph of the conditions at the time of the turbidity measurement. As shown in Figures 1 and 2, it was confirmed that water purification agents 1, 4, and 5 of the present invention exhibited sufficiently low turbidity and provided excellent water purification effects.

Claims

1. An organic coagulant containing plant extracts, The plant of the aforementioned plant extract is Ephedra sinica, The organic coagulant is characterized in that the Δ-zeta potential, measured and calculated as described below, is 50 mV or more. [measurement] To 600 mL of potassium fluoride aqueous solution, which has been adjusted to a potassium fluoride concentration of 500 ppm, 3.5 mL of 35% by mass calcium fluoride aqueous solution is added while stirring. Next, 5% by mass sulfuric acid is added while stirring to adjust the pH to 4.5 ± 0.25, and this is called solution A. Measure the zeta potential of liquid A. Take 100 mL of liquid A and add the organic coagulant to it at a concentration of 1% by mass while stirring at 500 rpm. After stopping the stirring, sample the supernatant and measure the zeta potential after adding the organic coagulant. The difference between the zeta potential of liquid A and the zeta potential after adding the organic coagulant is calculated as the Δzeta potential.

2. The organic coagulant according to claim 1, wherein the conductivity of the organic coagulant when the solid content is 0.1% by mass is 12 to 350 mS / m.

3. An organic coagulant according to any one of claims 1 to 2, wherein the zeta potential is anionic.

4. The organic coagulant according to any one of claims 1 to 3, wherein the plant extract contains water-soluble natural lignocellulose.

5. A method for producing an organic coagulant according to any one of claims 1 to 4, The grinding process for crushing plants, An extraction process in which crushed plants and water are mixed to obtain a plant extract, A filtration step of filtering the plant extract to obtain a liquid component, A method for producing an organic coagulant, characterized by containing [the specified ingredient].

6. The method for producing an organic coagulant according to claim 5, wherein the extraction step is performed under any of the following conditions: room temperature, heating, and heating and pressurizing.

7. An organic coagulant according to any one of claims 1 to 4, A water purification agent characterized by containing a polymer flocculant.

8. The water purification agent according to claim 7, which is a particle.

9. The water purification agent according to any one of claims 7 to 8, wherein the mass ratio (organic coagulant / polymer flocculant) of the organic coagulant to the polymer flocculant is 0.01 / 99.99 to 99.99 / 0.

01.

10. The water purification agent according to any one of claims 7 to 9, wherein the content of the water-insoluble component is 5% by mass or less.

11. A method for producing a water purification agent containing an organic coagulant and a polymer flocculant according to any one of claims 1 to 4, A kneading step to obtain a kneaded product by kneading the polymer flocculant and the organic coagulant according to any one of claims 1 to 4, A drying step in which the kneaded material is dried to obtain a dried product, A grinding step to obtain a pulverized product by grinding the aforementioned dried material, A classification step to obtain a water purification agent by classifying the aforementioned pulverized material, A method for producing a water purification agent, characterized by containing [the specified ingredient].

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