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

Abstract

Organic coagulants containing plant extracts, and water purifiers containing the above-mentioned organic coagulants and high-molecular coagulants, etc.

Description

Technical Field

[0001] This invention relates to organic coagulants and their manufacturing methods, as well as water purifiers and their manufacturing methods. Background Technology

[0002] In recent years, during the manufacturing of various products in factories and other facilities, a large amount of waste liquid containing environmentally burdensome substances such as metal ions and fluoride ions (which are inorganic ions) has been generated, and water purification treatment using water purification agents has been carried out.

[0003] To date, as a water purifier that flexibly utilizes the charge neutralization properties of plants, water purifiers formed from granules comprising a mixture of plant powder and a polymeric flocculant have been proposed (see, for example, Patent Document 1). The aforementioned technology is highly beneficial as it offers excellent water purification performance and is also suitable for use in automated wastewater purification devices.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2016-187782 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] As described above, the technology described in Patent Document 1 is highly advantageous. On the other hand, plants contain components that are insoluble in water; therefore, when used as a flocculant, a relatively high viscosity is required during dissolution to prevent the sedimentation of these insoluble components. Consequently, the range of product characteristics, such as the use of only high-viscosity materials or the composition ratio of the various components in the water purifier, is limited. Furthermore, if the viscosity is insufficient (low), the possibility of precipitated insoluble components clogging pipes is considered. Therefore, there is a strong demand for the rapid development of water purifiers with low content of insoluble components.

[0009] The objective of this invention is to solve the aforementioned problems and achieve the following objectives: Specifically, the objective of this invention is to provide a water purifier with low content of water-insoluble components and excellent water purification performance, as well as a method for manufacturing the same, and an organic coagulant suitable for use in the aforementioned water purifier, and a method for manufacturing the same.

[0010] Methods for solving problems

[0011] The inventors conducted in-depth research and discovered that by including plant extracts, excellent water purification properties are achieved while removing water-insoluble components from plants. Furthermore, it was found that components that precipitate when dissolved in water can be removed, thus enabling the creation of a low-viscosity material and significantly increasing the design flexibility of water purifiers, including viscosity and formulation ratios.

[0012] The method for solving the above-mentioned problem is as follows. That is,

[0013] <1> An organic coagulant, characterized in that it contains plant extracts.

[0014] <2> The conductivity of the organic coagulant described in <1> above is 12 to 350 mS / m when the content of the solid component in the organic coagulant is 0.1% by mass.

[0015] <3> The organic coagulant according to any one of <1> to <2> above has an anionic potential.

[0016] <4> The organic coagulant according to any one of <1> to <3> above, the above plant extract contains water-soluble natural lignocellulose.

[0017] <5> The organic coagulant according to any one of <1> to <4> above, wherein the plant from which the plant extract is derived is selected from at least one species selected from the group consisting of rice, reed and hemp.

[0018] <6> A method for manufacturing an organic coagulant, characterized in that it is a method for manufacturing the organic coagulant as described in any one of <1> to <5> above, comprising the following steps:

[0019] The crushing process that involves pulverizing plants;

[0020] The process of mixing pulverized plant material with water to obtain plant extracts; and

[0021] The above-mentioned plant extracts are filtered to obtain a liquid component.

[0022] <7> According to the method for manufacturing the organic coagulant described in <6> above, the above extraction process is carried out under any of the following conditions: room temperature, heating, and heating with pressure.

[0023] <8> A water purification agent, characterized in that it contains:

[0024] The organic coagulant described in any one of <1> to <5> above, and

[0025] Polymer flocculant.

[0026] <9> The water purifier described in <8> above is in the form of particles.

[0027] <10> In the water purification agent according to any one of <8> to <9> above, the mass ratio of the organic coagulant to the polymeric coagulant (organic coagulant / polymeric coagulant) is 0.01 / 99.99 to 99.99 / 0.01.

[0028] <11> The water purifier according to any one of <8> to <10> above has an insoluble component content of 5% by mass or less relative to water.

[0029] <12> A method for manufacturing a water purification agent, characterized in that it is a method for manufacturing a water purification agent containing any one of the organic coagulant and polymeric coagulant described in <1> to <5> above, comprising the following steps:

[0030] The mixing process of mixing the above-mentioned polymeric coagulant with any one of the organic coagulants in <1> to <5> to obtain a mixture;

[0031] The drying process of drying the above-mentioned mixture to obtain a dried product;

[0032] The pulverization process of pulverizing the above-mentioned dried material to obtain pulverized material; and

[0033] The above-mentioned pulverized material is graded to obtain a water purification agent.

[0034] The effects of the invention

[0035] According to the present invention, the aforementioned problems can be solved and the above-mentioned objectives can be achieved. A water purifier with low content of water-insoluble components and excellent water purification performance, as well as a method for manufacturing the same, can be provided. An organic coagulant suitable for use in the above-mentioned water purifier, as well as a method for manufacturing the same, can also be provided. Attached Figure Description

[0036] Figure 1 A graph showing the results of turbidity measurements in Test Examples 1-5.

[0037] Figure 2 The images were taken to capture the state of the samples when the turbidity of test examples 1 to 5 was measured. Detailed Implementation

[0038] (Organic coagulant)

[0039] The organic coagulant of the present invention contains at least plant extracts and may further contain other ingredients as needed.

[0040] <Plant Extracts>

[0041] There are no particular restrictions on the plants used as extracts; appropriate selection can be made according to the intended purpose. One of the aforementioned plants may be used alone, or two or more may be used in combination.

[0042] Of the aforementioned plants, preferably at least one is selected from the group consisting of rice, reeds and hemp.

[0043] As for the aforementioned types of hemp, there are no special restrictions, and appropriate selection can be made according to the purpose. Longshuo jute is a suitable example.

[0044] As for the aforementioned Changsha jute, preferred varieties include Changsha jute produced in Changsha, China; "Zhonghuangma No. 4" with identification number Guojianma 2013, "Zhonghuangma No. 3" with identification number Wanpin▲Jian▼Dengzi No. 1209006, "Zhonghuangma No. 1" with identification number XPD005-2005, or "Zhonghongma" with identification number Wanpin▲Jian▼Dengzi No. 1209001. Among these, "Zhonghuangma No. 4", "Zhonghuangma No. 3", and "Zhonghongma" are more preferred, and "Zhonghuangma No. 4" is particularly preferred.

[0045] The aforementioned "Zhonghuangma No. 4" has the following characteristics.

[0046] Agricultural products: jute

[0047] Origin of the variety: A variety bred from the F1 generation of a cross between Xianghuangma No. 3 × 0-4(l) and Xianghuangma No. 3.

[0048] Characteristics: Zhonghuangma No. 4 is a typical long-fruited jute variety with green, cylindrical stems. The leaves are scattered, needle-shaped with green petioles and a small angle with the main stem. It has lateral buds and stipules. The calyx is green, and the long, cylindrical fruit has five chambers. It is a late-maturing variety.

[0049] The above-mentioned plant extracts preferably contain water-soluble natural lignocellulose.

[0050] -Water-soluble natural lignocellulose-

[0051] The aforementioned water-soluble natural lignocellulose (hereinafter, sometimes referred to as "lignocellulose") is composed of cellulose, hemicellulose, and lignin. Lignin, along with polysaccharides (cellulose and hemicellulose), constitutes the main components of the cell walls of plants.

[0052] There are no particular restrictions on the content of the plant extracts containing the aforementioned lignocellulose, and they can be appropriately selected according to the purpose.

[0053] There are no particular limitations on the method for preparing the above-mentioned plant extracts. A known method for preparing plant extracts can be appropriately selected according to the purpose. It is preferred to prepare them by the extraction step in the method for manufacturing the organic coagulant of the present invention, which will be described later.

[0054] There are no particular restrictions on the content of organic coagulants used as the above-mentioned plant extracts, and they can be appropriately selected according to the purpose.

[0055] <Other Ingredients>

[0056] Other components in the above-mentioned organic coagulant are not particularly limited as long as they do not impair the effect of the present invention, and can be appropriately selected according to the purpose.

[0057] There are no particular restrictions on the content of the organic coagulant, which is one of the other components mentioned above, and it can be appropriately selected according to the purpose.

[0058] There are no particular limitations on the form of the aforementioned organic coagulant; it can be appropriately selected according to the purpose and can be either a liquid or a solid. The aforementioned organic coagulant can be manufactured as a liquid component, as described later, and can solidify the liquid component for use by dissolving it in water.

[0059] <Viscosity>

[0060] There are no particular limitations on the viscosity of the aforementioned organic coagulant, and it can be appropriately selected according to the purpose. For example, the viscosity of an aqueous solution with a solid content of 0.1% by mass can be 0.5 to 5 mPa·s.

[0061] The above viscosity can be measured using a TVC-10 viscometer (Type B viscometer) manufactured by Toki Sangyo, at 23°C using a rotor of type 0.

[0062] <Conductivity>

[0063] The conductivity of the aforementioned organic coagulant is not particularly limited and can be appropriately selected according to the purpose. When the conductivity is an aqueous solution with a solid content of 0.1% by mass, it is preferably 12 to 350 mS / m, and more preferably 50 to 350 mS / m.

[0064] The above conductivity can be measured at a liquid temperature of 22°C using a conductivity meter: F-70 desktop type (manufactured by Horiba Corporation).

[0065] <Boundary potential>

[0066] There are no particular limitations on the threshold potential of the aforementioned organic coagulants; they can be appropriately selected according to the purpose, with anionicity being preferred.

[0067] Furthermore, when the above-mentioned organic coagulant is measured as described below, the calculated Δ boundary potential is preferably 40 mV or more, more preferably 45 mV, and particularly preferably 50 mV or more.

[0068] [Measurement]

[0069] Add 600 mL of a potassium fluoride aqueous solution with a concentration adjusted to 500 ppm to a beaker, and while stirring further, add 3.5 mL of a 35% (w / w) calcium fluoride aqueous solution.

[0070] Next, while stirring well, add 5% sulfuric acid by mass to adjust the pH to 4.5 ± 0.25.

[0071] The threshold potential of the liquid whose pH has been adjusted as described above is measured (hereinafter, sometimes referred to as "CaF2 threshold potential").

[0072] In addition, 100 mL of the pH-adjusted liquid was collected and added while stirring at 500 rpm to achieve a concentration of 1% by mass of the organic coagulant. After stirring was stopped, the supernatant was sampled, and the threshold potential (hereinafter sometimes referred to as "threshold potential after addition of organic coagulant") was measured.

[0073] The difference between the CaF2 threshold potential (A) and the threshold potential (B) after the addition of the organic coagulant is used as the Δ threshold potential for calculation.

[0074] The aforementioned threshold potential can be determined using the dynamic scattering method.

[0075] The above-mentioned organic coagulant can be suitably manufactured by the method for manufacturing the organic coagulant of the present invention, which will be described later.

[0076] As shown in the examples described later, the aforementioned organic coagulant exhibits excellent flocculant properties and can therefore be used in combination with polymeric coagulants for water purification. Furthermore, the aforementioned water purification can be performed without the use of inorganic coagulants such as aluminum-based inorganic coagulants, iron-based inorganic coagulants, or slaked lime. The aforementioned organic coagulant is suitable for use in the water purification agent of the present invention described later.

[0077] (Method for manufacturing organic coagulants)

[0078] The method for manufacturing the organic coagulant of the present invention is as described above, and includes at least a pulverizing step, an extraction step, and a filtration step, and may further include other steps as needed.

[0079] <Pulverizing Process>

[0080] The above-mentioned crushing process is a process of crushing plants.

[0081] There are no particular restrictions on the parts of the aforementioned plants (hereinafter sometimes referred to as "extractable materials"), and they can be appropriately selected according to the purpose; for example, leaves, stems, and bark can be used. One type can be used alone, or two or more types can be used together.

[0082] The raw materials used for extraction can be dried or undried, but dried is preferred.

[0083] There are no particular restrictions on the methods for pulverizing plants as described above; any known method can be appropriately selected.

[0084] There are no particular limitations on the degree of pulverization mentioned above, and it can be appropriately selected according to the purpose.

[0085] <Extraction Process>

[0086] The above extraction process involves mixing pulverized plant material with water to obtain plant extracts.

[0087] The number of extraction steps mentioned above can be one or more times.

[0088] The above extraction process only requires at least one extraction using water as the extraction solvent. Extraction can be performed using organic solvents such as ethyl acetate, but it is preferred to use only water for extraction.

[0089] There are no particular restrictions on the types of water mentioned above; appropriate selection can be made according to the purpose. For example, pure water can be cited.

[0090] In the above extraction process, the pulverized plant material can be added to the extraction solvent, and vice versa. Furthermore, stirring can be performed as needed during the extraction process.

[0091] There are no particular restrictions on the concentration of the extraction raw material used in the above extraction process, and it can be appropriately selected according to the purpose. For example, 1 to 10% by mass can be used.

[0092] There are no particular restrictions on the temperature and pressure used in the above extraction process, and they can be appropriately selected according to the purpose. For example, room temperature, heating, and heating with pressure are all acceptable options.

[0093] The above-mentioned normal temperature refers to approximately 20–28℃.

[0094] The heating mentioned above refers to a temperature higher than the ambient temperature mentioned above.

[0095] The heating and pressurization mentioned above refers to a temperature higher than the ambient temperature and a pressure higher than the ambient pressure. For example, the pressure higher than the ambient pressure can be about 2 atm.

[0096] There are no particular restrictions on the extraction time mentioned above; it can be selected appropriately according to the purpose. For example, it can be 10 minutes to 24 hours.

[0097] There are no particular limitations on the method for confirming whether the above-mentioned plant extracts contain lignocellulose. Well-known methods can be appropriately selected, such as the method for confirming by detecting the decomposition products obtained by thermal decomposition GC-MS.

[0098] <Filtration Process>

[0099] The above-mentioned filtration process is the process of filtering the above-mentioned plant extract to obtain a liquid component (hereinafter, sometimes referred to as "filtrate").

[0100] By performing the above filtration, it is possible to obtain plant extracts that do not contain components that are insoluble in water.

[0101] There are no particular restrictions on the filtering methods mentioned above, and well-known methods can be appropriately selected.

[0102] There are no particular restrictions on the amount of solid component in the above-mentioned liquid components, and it can be appropriately selected according to the purpose. For example, 0.05 to 2% by mass can be cited.

[0103] There are no particular limitations on the method for determining the amount of the above-mentioned solid components, and it can be appropriately selected according to the purpose. For example, the above-mentioned filtrate can be dried and the amount of the resulting solidified product can be calculated.

[0104] <Other Processes>

[0105] As for the other steps mentioned above, there are no particular limitations as long as they do not impair the effect of the present invention, and they can be appropriately selected according to the purpose.

[0106] (Water purification agent)

[0107] The water purifier of the present invention comprises at least the organic coagulant and the polymeric coagulant of the present invention, and may further comprise other components as needed.

[0108] <Organic coagulant>

[0109] The above-mentioned organic coagulant uses the organic coagulant of the present invention.

[0110] There are no particular restrictions on the content of the aforementioned organic coagulant in the water purifier, and it can be appropriately selected according to the purpose. By adjusting the content of the aforementioned organic coagulant, the amount of plant extract in the water purifier can be adjusted.

[0111] <Polymer flocculants>

[0112] As for the aforementioned polymeric flocculant, there are no particular limitations if it is a polymeric flocculant that demonstrates the effect of removing the aforementioned inorganic waste from wastewater, and it can be appropriately selected according to the purpose. For example, polymers containing acrylamide (“polyacrylamide”, sometimes simply “PAM”), polyamines, sodium alginate, sodium polyacrylate, sodium carboxymethyl cellulose (CMC) salt, etc., can be mentioned. Among these, polymers containing acrylamide, polyacrylamide, and sodium polyacrylate are preferred.

[0113] The aforementioned polymeric flocculants can have ionic structures. Examples of cations include ammonium salts and sulfonium salts. Examples of anions include carboxylates.

[0114] The above-mentioned polymeric flocculants can be used alone or in combination with two or more.

[0115] There are no particular restrictions on the content of the aforementioned polymeric coagulant in water purification agents, and it can be appropriately selected according to the purpose.

[0116] Commercially available products can be used as the aforementioned polyacrylamide. Examples of such commercially available products include Flopam AN905, Flopam AN 926, and Flopam AN 956 (all manufactured by SNF Corporation); ACCOFLOCA A-100 and ACCOFLOCAA-150 (both manufactured by MT Aquapolymer Corporation).

[0117] Sodium polyacrylate can be commercially available products, such as ACCOFLOCA A-190 (manufactured by MT Aquapolymer Co., Ltd.) and PA-331 (manufactured by Kurita Kogyo Co., Ltd.).

[0118] The mass ratio of the organic coagulant to the polymeric coagulant (organic coagulant / polymeric coagulant) is not particularly limited and can be appropriately selected according to the purpose, preferably 0.01 / 99.99 to 99.99 / 0.01. If within the above preferred range, excellent water purification performance with sufficient adsorption effect of the microfibers is achieved. Furthermore, in this invention, the mass ratio of the organic coagulant to the polymeric coagulant is calculated based on the dry mass of each component.

[0119] <Other Ingredients>

[0120] Other components in the aforementioned water purification agent are not particularly limited and can be appropriately selected according to the purpose, provided they do not impair the effects of the present invention. Examples include preservatives, fillers, thickeners, colorants, thixotropic agents, and other additives. One of these can be used alone, or two or more can be used in combination.

[0121] There are no particular restrictions on the content of the other components in the water purification agent, and they can be appropriately selected according to the purpose.

[0122] The shape of the aforementioned water purifier is not particularly limited and can be appropriately selected according to the purpose, with particles (hereinafter sometimes referred to as "granules" or "granules") being preferred.

[0123] The content of the insoluble component in the above-mentioned water purifier relative to water is not particularly limited and can be appropriately selected according to the purpose. It is preferably 5% by mass or less, and more preferably does not contain any insoluble component relative to water.

[0124] The above-mentioned components that are insoluble relative to water refer to those that do not dissolve in pure water at 25°C under the condition of stirring at 500 rpm for 30 minutes.

[0125] There are no particular limitations on the method for calculating the content of the insoluble components relative to water, and it can be appropriately selected according to the purpose. For example, the solution can be centrifuged at a centrifugal force of 2,500G for 5 minutes to remove the supernatant, and the weight of the dried residue can be measured. The content of the insoluble components in the water purifier relative to water can be calculated from this value.

[0126] There are no particular limitations on the manufacturing method of the above-mentioned water purifier, and it can be appropriately selected according to the purpose. It is preferred to manufacture it by the water purifier manufacturing method of the present invention described later.

[0127] As shown in the examples described later, the aforementioned water purifier reduces the water-insoluble components contained in plants while exhibiting excellent water purification effects. Therefore, it can be made into a low-viscosity material, significantly increasing the design freedom in terms of viscosity, formulation ratios, and other aspects of the water purifier.

[0128] (Manufacturing method of water purification agent)

[0129] The method for manufacturing the water purifier of the present invention is a method for manufacturing a water purifier containing the organic coagulant and the polymeric coagulant of the present invention, which includes at least a mixing process, a drying process, a pulverizing process and a grading process, and may further include other processes such as a molding process as needed.

[0130] <Mixing Process>

[0131] The above-mentioned mixing process is a process of mixing the above-mentioned polymeric coagulant with the organic coagulant of the present invention to obtain a mixture.

[0132] There are no particular limitations on the above-mentioned mixing method, and it can be appropriately selected according to the purpose. For example, a method of mixing can be described by adding a liquid organic coagulant to the above-mentioned polymeric coagulant. Water can be added as needed in the above-mentioned mixing process.

[0133] Mixing is performed using a mixer, such as a planetary mixer or a vertical mixer, with the speed and time set within a predetermined range.

[0134] The speed and time of mixing in the mixer can be appropriately set while taking into account conditions such as the mixing ratio of organic coagulant and polymeric coagulant. For example, the speed is preferably 20 rpm to 150 rpm and the time is preferably 5 minutes to 25 minutes.

[0135] <Drying Process>

[0136] The above-mentioned drying process is a process of drying the above-mentioned mixture to obtain a dried product.

[0137] Between the above-mentioned mixing process and the above-mentioned drying process, there may be a forming process (sometimes referred to as "stretching, sheeting process") to obtain a molded article in which the above-mentioned mixture is shaped into a sheet.

[0138] In the above molding process, the obtained mixture can be stretched using a roller to make the thickness 2mm to 30mm, preferably about 10mm, and then formed into a sheet.

[0139] In the above drying process, the above-mentioned mixture or the above-mentioned molded product can be dried in a multi-stage hot air dryer at a temperature of 80℃~150℃ for 2 hours to 12 hours.

[0140] <Pulverizing Process>

[0141] The above-mentioned pulverizing process is a process of pulverizing the above-mentioned dried material to obtain pulverized material.

[0142] In the above-mentioned pulverization process, a pulverizer, such as an airflow ultrafine pulverizer, can be used to pulverize the particles in a manner with a median particle size ranging from 150 μm to 900 μm.

[0143] <Grading Process>

[0144] The above-mentioned grading process is a process of grading the above-mentioned pulverized material to obtain a water purifier.

[0145] In the above grading process, a grading machine, such as a vibrating screen or a box sieve, can be used to classify the pulverized powder into granules with a median particle size of 150μm to 900μm, thus classifying the granules with a particle size within a predetermined range.

[0146] <Other Processes>

[0147] As for the other steps mentioned above, there are no particular limitations as long as they do not impair the effect of the present invention, and they can be appropriately selected according to the purpose. For example, the molding steps mentioned above can be cited.

[0148] The above manufacturing method enables the production of granular water purifiers.

[0149] (Water purification methods)

[0150] This invention relates to a water purification method using the water purifier of this invention.

[0151] The above water purification method dissolves the above water purification agent in water to obtain a dispersion of organic coagulant and polymeric coagulant, and supplies the above dispersion to the drainage, thereby removing inorganic waste from the drainage.

[0152] Examples of inorganic wastes mentioned above include nickel, fluorine, iron, copper, zinc, chromium, arsenic, cadmium, tin, and lead. These may contain only one or more of these elements.

[0153] The above water purification methods will be explained in detail.

[0154] An inorganic coagulant is added to inorganic wastewater containing inorganic ions such as nickel, fluoride, iron, copper, zinc, chromium, arsenic, cadmium, tin, and lead to form microfibers. This dispersion is then supplied to the wastewater as a 0.05% to 0.2% (w / w) aqueous solution. The microfibers agglomerate and settle, and the separated precipitate is removed, thus purifying the wastewater.

[0155] In the above-mentioned insoluble treatment, for example, it is preferable to add alkali to the wastewater to make the wastewater alkaline, and then add an inorganic coagulant to make the inorganic ions insoluble.

[0156] Examples of inorganic flocculants include ferrous chloride, polyferrous sulfate, ferrous sulfate, aluminum sulfate, polyaluminum chloride (PAC), and slaked lime. These can be used individually or in combination of two or more.

[0157] Example

[0158] The following describes embodiments of the present invention, etc., but the present invention is not limited to these embodiments, etc.

[0159] (Example 1: Organic coagulant 1)

[0160] <Manufacturing of Organic Coagulant 1>

[0161] The raw material used for extraction was the dried leaves of “Zhonghuangma No. 4” (identification number 2013) from the Institute of Bast Fiber Crops, Chinese Academy of Agricultural Sciences, and the extraction solvent was pure water, as described below.

[0162] The above-mentioned raw materials are dried by sunlight until the moisture content is less than 5% by mass, and then pulverized by an atomizer (hammer mill, manufactured by Masukuni Sangyo Co., Ltd.) to further use only substances with a particle size in the range of 100μm to 400μm.

[0163] -extract-

[0164] The above-mentioned raw material was added to the pure water to achieve a concentration of 4% by mass, stirred, and extracted under the following extraction conditions. After filtration, a filtrate with insoluble components removed was obtained (solid content: 1.3% by mass). The above-mentioned solid content was calculated from the amount of solidified product obtained by drying the above-mentioned filtrate in an oven.

[0165] [Extraction Conditions]

[0166] Temperature: 25℃

[0167] Time: 60 minutes

[0168] Pressure: Atmospheric pressure (operation without pressure)

[0169] The above filtrate was diluted with pure water to make the solid content 0.1% by mass, thus preparing organic coagulant 1.

[0170] <Evaluation>

[0171] -Viscosity-

[0172] The viscosity of the above-mentioned organic coagulant 1 was measured at 23°C using a TVC-10 viscometer (Type B viscometer) manufactured by Toki Sangyo Corporation, with rotor No. 0.

[0173] -Conductivity-

[0174] The conductivity of the above-mentioned organic coagulant 1 was measured at a liquid temperature of 22°C using a conductivity meter: a desktop F-70 (manufactured by Horiba Manufacturing Co., Ltd.).

[0175] -Jida Potential-

[0176] Add 600 mL of a potassium fluoride aqueous solution with a concentration adjusted to 500 ppm to a beaker, and while stirring thoroughly, add 3.5 mL of a 35% (w / w) calcium fluoride aqueous solution.

[0177] Next, add 5% sulfuric acid by mass while stirring thoroughly to adjust the pH to 4.5 ± 0.25.

[0178] The potential of arrival (hereinafter, sometimes referred to as "CaF2 potential of arrival") of the pH-adjusted liquid was determined using a Zetasizer Nano ZSP (made by Malvern Panalytical).

[0179] In addition, 100 mL of the pH-adjusted liquid was collected and added to a concentration of 1% by mass while stirring at 500 rpm. After stirring was stopped, the supernatant was sampled and the same procedure was performed to determine the threshold potential (hereinafter sometimes referred to as "threshold potential after addition of organic coagulant").

[0180] The difference between the CaF2 threshold potential (A) and the threshold potential (B) after the addition of the organic coagulant is used as the Δ threshold potential to calculate the coagulation performance using charge neutralization.

[0181] -Water purification treatment-

[0182] As wastewater to be treated, 600 mL of fluoride-treated water (fluoride concentration 500 mg / L) was used.

[0183] Next, 3.5 mL of 35% CaCl2 and 100 mg / L of the above-mentioned organic coagulant 1 were added to the above-mentioned wastewater, while stirring (adjusting the pH to 7.5) with 5% NaOH added. Through this operation, the wastewater was separated into a supernatant containing short fibers and a precipitate.

[0184] Next, for the drainage formed from the supernatant containing the micro-short fibers and the precipitate, add 2 mg / L of anionic polymeric flocculant (KURIFLOCK PA-331 (manufactured by Kurita Kogyo Co., Ltd.)), maintain stirring for 1 minute, and then proceed as follows to determine the "fluorine (F) concentration".

[0185] --Determination of Fluorine Concentration--

[0186] Two minutes after the sampling and stirring were stopped, the supernatant was tested using a digital pack (manufactured by Kyoritsu Chemical Research Institute Co., Ltd.) of a digital water quality analyzer that utilizes the lanthanum-alizarin complex spectrophotometry method to determine the fluoride concentration.

[0187] (Example 2: Organic coagulant 2)

[0188] <Manufacturing of Organic Coagulant 2>

[0189] The extraction conditions in the "Preparation of Organic Coagulant 1" of Example 1 were set as follows, except that the operation was the same as in Example 1, and a filtrate (solid content: 1.6% by mass) was obtained.

[0190] [Extraction Conditions]

[0191] Temperature 70℃

[0192] Time: 60 minutes

[0193] Pressure: Atmospheric pressure (operation without pressure)

[0194] Next, the above filtrate is diluted with pure water to make the solid content 0.1% by mass, thus preparing organic coagulant 2.

[0195] <Evaluation>

[0196] The same procedure as in the <Evaluation> section of Example 1 above was followed, and the viscosity, conductivity, threshold potential, and water purification treatment were evaluated.

[0197] (Example 3: Organic coagulant 3)

[0198] <Manufacturing of Organic Coagulant 3>

[0199] The extraction conditions in the "Preparation of Organic Coagulant 1" of Example 1 were set as follows, except that the operation was the same as in Example 1, and a filtrate (solid content: 3.5% by mass) was obtained.

[0200] [Extraction Conditions]

[0201] Temperature 100℃

[0202] Time: 60 minutes

[0203] Pressure: Atmospheric pressure (operation without pressure)

[0204] Next, the filtrate is diluted with pure water to make the solid content of the filtrate 0.1% by mass, thus preparing organic coagulant 3.

[0205] <Evaluation>

[0206] The same procedure as in the <Evaluation> section of Example 1 above was followed, and the viscosity, conductivity, threshold potential, and water purification treatment were evaluated.

[0207] (Example 4: Organic coagulant 4)

[0208] <Manufacturing of Organic Coagulant 4>

[0209] The extraction conditions in the "Preparation of Organic Coagulant 1" of Example 1 were set as follows, except that the operation was the same as in Example 1, and a filtrate (solid content: 4.5% by mass) was obtained.

[0210] [Extraction Conditions]

[0211] Temperature: 130℃

[0212] Time: 60 minutes

[0213] Pressure 2 atm

[0214] Next, the filtrate is diluted with pure water to make the solid content of the above filtrate 0.1% by mass, thus preparing organic coagulant 4.

[0215] <Evaluation>

[0216] The same procedure as in the <Evaluation> section of Example 1 above was followed, and the viscosity, conductivity, threshold potential, and water purification treatment were evaluated.

[0217] (Example 5: Organic coagulant 5)

[0218] <Manufacturing of Organic Coagulant 5>

[0219] The extraction raw materials and extraction conditions in the <Preparation of Organic Coagulant 1> of Example 1 were set as follows, except that the operation was the same as in Example 1 above, and a filtrate (solid content: 0.06% by mass) was obtained.

[0220] [Extracting raw materials]

[0221] The dried product of all parts (stem, bark, and leaves) of "Zhonghuangma No. 4" (identification number 2013, Institute of Bast Fiber Crops, Chinese Academy of Agricultural Sciences), was extracted from Jute. The raw material was dried under sunlight until the moisture content was below 5% by mass. Then, it was pulverized using an atomizer (hammer mill, manufactured by Masukuni Sangyo Co., Ltd.) to further refine the material to particles with a diameter ranging from 100 μm to 400 μm.

[0222] [Extraction Conditions]

[0223] Temperature: 25℃

[0224] Time: 60 minutes

[0225] Pressure: Atmospheric pressure (operation without pressure)

[0226] Next, the filtrate is concentrated under reduced pressure to obtain an organic coagulant 5, with the solid content of the filtrate being 0.1% by mass.

[0227] <Evaluation>

[0228] The same procedure as in the <Evaluation> section of Example 1 above was followed, and the viscosity, conductivity, threshold potential, and water purification treatment were evaluated.

[0229] (Example 6: Organic coagulant 6)

[0230] <Manufacturing of Organic Coagulant 6>

[0231] The raw material for extraction was the dried leaves of "Zhonghuangma No. 4" (identification number 2013) from the Institute of Bast Fiber Crops, Chinese Academy of Agricultural Sciences, and was extracted as described below.

[0232] The above-mentioned raw materials are dried by sunlight until the moisture content is less than 5% by mass, and then pulverized by an atomizer (hammer mill, manufactured by Masukuni Sangyo Co., Ltd.) to further use only substances with a particle size in the range of 100μm to 400μm.

[0233] -extract-

[0234] Ethyl acetate was added to the above-mentioned raw material to prepare a 10% by mass solution, which was then allowed to stand at room temperature (23°C) for 8 hours and filtered. The residue was washed with ethyl acetate. Then, the residue was further extracted with pure water (temperature: 25°C, time: 60 minutes, pressure: atmospheric pressure (no pressure operation)) to obtain a supernatant. The supernatant was then subjected to dialysis to separate components with a molecular weight cutoff of 12,000 or higher.

[0235] Organic coagulant 6 was prepared by vacuum concentration to reduce the amount of solid components in the separated solution to 0.1% by mass.

[0236] <Evaluation>

[0237] The same procedure as in the <Evaluation> section of Example 1 above was followed, and the viscosity, conductivity, threshold potential, and water purification treatment were evaluated.

[0238] (Example 7: Organic coagulant 7)

[0239] <Manufacturing of Organic Coagulant 7>

[0240] The component with a molecular weight cutoff of less than 12,000 obtained by the dialysis operation in the <Manufacturing of Organic Coagulant 6> of Example 6 above is further dialyzed to obtain a component with a molecular weight cutoff of less than 6,000. The component with a molecular weight cutoff of less than 6,000 is further dialyzed to separate a component with a molecular weight cutoff of less than 3,000.

[0241] To obtain organic coagulant 7, the solution was concentrated under reduced pressure so that the amount of solid components in the separated solution was 0.1% by mass.

[0242] <Evaluation>

[0243] The same procedure as in the <Evaluation> section of Example 1 above was followed, and the viscosity, conductivity, threshold potential, and water purification treatment were evaluated.

[0244] (Comparative Example 1: Inorganic Flocculant)

[0245] <Evaluation>

[0246] -Water purification treatment-

[0247] In the water purification treatment of Example 1 above, the addition of 100 mg / L organic coagulant 1 was changed to the addition of 8% by mass Al2(SO4)3·16H2O32 mg / L. Otherwise, the water purification treatment was carried out in the same manner as in Example 1.

[0248] (Comparative Example 2: No organic or inorganic coagulants)

[0249] <Evaluation>

[0250] -Water purification treatment-

[0251] The organic coagulant 1 used in the water purification treatment of Example 1 was not used; otherwise, the water purification treatment was performed in the same manner as in Example 1.

[0252] (Comparative Example 3: Comparison with Coagulant 1)

[0253] <Comparative manufacturing of coagulant 1>

[0254] The raw material was dried rice husks, and the extraction solvent was pure water. The extraction was carried out as described below.

[0255] The above-mentioned raw materials are dried by sun drying until the moisture content is less than 5% by mass, and then pulverized by atomizer (hammer mill, manufactured by Masukuni Sangyo Co., Ltd.) to further use only substances with a particle size in the range of 100μm to 400μm.

[0256] -extract-

[0257] The above-mentioned raw material was added to the pure water to achieve a concentration of 4% by mass, stirred, and extracted under the following extraction conditions. After filtration, a filtrate with insoluble components removed was obtained (solid content: 0.005% by mass).

[0258] [Extraction Conditions]

[0259] Temperature 95℃

[0260] Time: 60 minutes

[0261] Pressure: Atmospheric pressure (operation without pressure)

[0262] Next, the filtrate was concentrated under reduced pressure to obtain a comparative coagulant 1, with the solid content of the filtrate being 0.1% by mass.

[0263] <Evaluation>

[0264] The same procedure as in the <Evaluation> section of Example 1 above was followed, and the viscosity, conductivity, threshold potential, and water purification treatment were evaluated.

[0265] (Comparative Example 4: Comparison of Coagulant 2)

[0266] <Comparative manufacturing of coagulant 2>

[0267] The extraction conditions in the “Preparation of Comparative Coagulant 1” of Comparative Example 3 were set as follows, and the operation was carried out in the same manner as in Comparative Example 3 to obtain a filtrate (solid content: 0.015% by mass).

[0268] [Extraction Conditions]

[0269] Temperature: 130℃

[0270] Time: 60 minutes

[0271] Pressure 2 atm

[0272] Next, the filtrate was concentrated under reduced pressure to obtain a comparative coagulant 2, with the solid content of the filtrate being 0.1% by mass.

[0273] <Evaluation>

[0274] The same procedure as in the <Evaluation> section of Example 1 above was followed, and the viscosity, conductivity, threshold potential, and water purification treatment were evaluated.

[0275] The results of Examples 1 to 7 and Comparative Examples 1 to 4 described above are shown in Tables 1 and 2 below.

[0276] [Table 1]

[0277]

[0278] The “※” in Table 1 refers to paragraph

[0084] .

[0279] [Table 2]

[0280]

[0281] As shown in Tables 1 and 2, when the organic coagulant of the present invention was used, it was confirmed that the fluoride concentration in the supernatant after water purification was reduced.

[0282] (Experimental Example 1: Water Purifying Agent 1)

[0283] <Manufacturing of Water Purifier 1>

[0284] Using the organic coagulant 5 from Example 5 above, granular water purifier 1 was manufactured as follows.

[0285] The mixture obtained by adding 5% by mass of the above organic coagulant 5 to the polymer coagulant (AN926VHM (manufactured by SNF Corporation)) (polymer coagulant + organic coagulant = 30kg) is placed in a planetary mixer (manufactured by Aikosha Co., Ltd., mixer ACM-110, capacity 110L) and kneaded using a blade at a speed of 150rpm for 20 minutes.

[0286] The obtained mixture is stretched using a press (manufactured by Komatsu Corporation, 45t press) to produce sheet-like molded parts with a thickness of about 10mm.

[0287] The molded material was dried at 120°C for 3 hours using a multi-stage hot air dryer (manufactured by Nanayo Co., Ltd., rack-type drying oven device), and then further dried at 150°C for 2 hours.

[0288] Next, the dried flakes were pulverized using an airflow ultrafine pulverizer (manufactured by Masukuni Sangyo Co., Ltd., CerenMiller) to achieve a median particle size of 400 μm. The median particle size was measured using a master sizer 2000 (manufactured by Malvern Instruments).

[0289] The pulverized powder is sieved using a classifier (Dalton Corporation, vibrating sieve) to remove particles smaller than 200 μm and larger than 900 μm, so that only materials with particle sizes in the range of 200 μm to 900 μm are used.

[0290] This process yields granules, which are then used to produce water purification agent 1. The insoluble components in the water purification agent 1 have a content of less than 5% by mass relative to water.

[0291] <Evaluation>

[0292] -Turbidity-

[0293] As part of the test drainage, 500 mL of a solution containing kaolinite (kaolinite concentration 50 ppm) was used.

[0294] Next, add 0.07 mL of 10% polyaluminum chloride (PAC) to the above drainage and adjust the pH to 7-8 using 0.21 mL of 5% sodium hydroxide.

[0295] Then, 1.5 mL of an aqueous solution containing 0.1% by mass of the above water purifier 1 was added, and the turbidity of the supernatant was measured within 10 seconds after addition. The determination was performed according to JIS K 0101:1998 (Test Method 9.2 Transmitted Turbidity of Industrial Water) using a HACH DR 3900 spectrophotometer.

[0296] (Experimental Example 2: Water Purification Agent 2)

[0297] <Manufacturing of Water Purifier 2>

[0298] The mixture of polymeric flocculant and organic coagulant 5 in Test Example 1 was replaced with a mixture of three times the mass of water relative to the total mass of the extracted raw material (plant powder) and polymeric flocculant (AN926VHM (manufactured by SNF Corporation)) used in the manufacture of the organic coagulant 5, resulting in a mixture (plant powder + polymeric flocculant + water = 30 kg). Water purification agent 2 was manufactured using the same procedure as in Test Example 1. The insoluble component in water purification agent 2 was 20% by mass relative to water.

[0299] <Evaluation>

[0300] The same procedure as in Experiment 1 above was followed to measure the turbidity.

[0301] (Experimental Example 3: Water Purification Agent 3)

[0302] <Manufacturing of Water Purifier 3>

[0303] Water purifier 3 was manufactured without using the plant powder from Test Example 2, but otherwise operated in the same manner as in Test Example 2. Water purifier 3 does not contain any components that are insoluble in water.

[0304] <Evaluation>

[0305] The same procedure as in Experiment 1 above was followed to measure the turbidity.

[0306] (Experimental Example 4: Water Purification Agent 4)

[0307] <Manufacturing of Water Purifier 4>

[0308] The organic coagulant 5 in Test Example 1 was replaced with the organic coagulant 6 in Example 6, and the water purifier 4 was manufactured in the same manner as in Test Example 1. The content of the insoluble components in the water purifier 4 was 5% by mass or less.

[0309] <Evaluation>

[0310] The same procedure as in Experiment 1 above was followed to measure the turbidity.

[0311] (Experimental Example 5: Water Purification Agent 5)

[0312] <Manufacturing of Water Purifier 5>

[0313] The organic coagulant 5 in Test Example 1 was replaced with the organic coagulant 7 in Example 7, and the water purification agent 5 was manufactured in the same manner as in Test Example 1. The content of the insoluble components in the water purification agent 5 was 5% by mass or less.

[0314] <Evaluation>

[0315] The same procedure as in Experiment 1 above was followed to measure the turbidity.

[0316] The results of the above test examples 1 to 5 are shown in Figure 1 and Figure 2 . Figure 1 A graph showing the results of the turbidity measurement. Figure 2 This image was taken to capture the state of the turbidity during measurement.

[0317] Figure 1 and Figure 2 As shown, it has been confirmed that water purifiers 1, 4, and 5, which are water purifiers of the present invention, have sufficiently low turbidity and exhibit excellent water purification effects.

Claims

1. An organic coagulant, characterized in that, Contains plant extracts, The plant from which the plant extract is extracted is Jute. The plant extract contains water-soluble natural lignocellulose. The conductivity of the organic coagulant is 50 mS / m to 350 mS / m when the content of the solid component in the organic coagulant is 0.1% by mass.

2. The organic coagulant according to claim 1, wherein, The Δ threshold potential of the organic coagulant, measured and calculated in the following manner, is above 50 mV: Add 3.5 mL of 35% calcium fluoride aqueous solution to 600 mL of potassium fluoride aqueous solution with the concentration adjusted to 500 ppm while stirring. Then, while stirring the resulting mixture, add 5% sulfuric acid to adjust the pH to 4.5 ± 0.25 to prepare liquid A. The potential of arrival of liquid A is measured; Collect 100 mL of liquid A, and while stirring liquid A at 500 rpm, add the organic coagulant to make the concentration of the organic coagulant 1% by mass. After the stirring is completed, take a sample of the supernatant and then measure the threshold potential after adding the organic coagulant. The difference between the potential of arrival of liquid A and the potential of arrival after the addition of the organic coagulant is used as Δpotential of arrival.

3. The organic coagulant according to claim 1 or 2, The organic coagulant is used for water purification treatment without the use of inorganic coagulants.

4. A method for manufacturing an organic coagulant, characterized in that, A method for manufacturing the organic coagulant according to any one of claims 1 to 3 includes the following steps: The crushing process that involves pulverizing plants; The process of mixing pulverized plant material with water to obtain plant extracts; and The filtration process involves filtering the plant extract to obtain a liquid component.

5. The method for manufacturing the organic coagulant according to claim 4, The extraction process can be carried out under any of the following conditions: room temperature, heating, or heating under pressure.

6. A water purification agent, characterized in that, contain: The organic coagulant according to any one of claims 1 to 3, and Polymer flocculant.

7. The water purifying agent according to claim 6, wherein it is in the form of particles.

8. The water purifying agent according to claim 6 or 7, The mass ratio of the organic coagulant to the polymeric coagulant, i.e., organic coagulant / polymeric coagulant, is 0.01 / 99.99 to 99.99 / 0.

01.

9. The water purifying agent according to claim 6 or 7, The insoluble components in the water purifier are less than 5% by mass relative to the water content.

10. A method for manufacturing a water purification agent, characterized in that, A method for manufacturing a water purification agent containing any one of the organic coagulant and polymeric coagulant according to claims 1 to 3, comprising the following steps: The mixing process of mixing the polymeric coagulant with the organic coagulant according to any one of claims 1 to 3 to obtain a mixture; The drying process of drying the mixture to obtain a dried product; The process of pulverizing the dried material to obtain pulverized material; and The grading process involves classifying the pulverized material to obtain a water purification agent.

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