JP6531416B2 - Method of measuring polymer concentration in water and water treatment method - Google Patents

Description

  The present invention relates to a method for measuring the concentration of a polymer in water and a method for treating water, and in particular, in permeable water treatment such as seawater desalination, ultrapure water production, industrial water treatment, drainage recovery treatment, etc. The present invention relates to a method of accurately measuring the concentration of a biometabolic polymer in water considered to contaminate functional materials of the above, and a water treatment method of controlling the amount of coagulant added based on the measurement result.

  Among organic substances contained in raw water for water treatment, it is known that, particularly, polymers of biological metabolites such as polysaccharides and proteins significantly contaminate microfiltration membranes, ultrafiltration membranes or reverse osmosis membranes. It is common practice to remove high molecular weight organic substances in raw water by coagulation treatment and the like.

  In the aggregation treatment, inorganic coagulants such as iron chloride, polyaluminum chloride (PAC) and polyferric sulfate are used. Patent Documents 1 and 2 propose a flocculant using a phenolic resin as an aggregating agent for enhancing the removal effect of macromolecules of biological metabolite type. Furthermore, as in Patent Document 3 (Japanese Patent Publication No. 2-15243), one using a melamine-based resin as a coagulant for organic drainage is also used.

  It is necessary to increase the addition amount of the inorganic flocculant and the above-mentioned flocculating agent when the concentration of the biological metabolite type polymer of raw water becomes high. In order to operate the water treatment apparatus stably, it is necessary to measure the concentration of the biometabolic polymer of the raw water, and to control the addition amount of the inorganic flocculant and the flocculating agent according to the concentration.

  The phenol sulfuric acid method is known as a method for measuring the concentration of saccharides in water, but the concentration range that can be measured well is 10 to 100 mg / L, and it is suitable for measuring the concentration of saccharides of 1 mg / L or less There is no (for example, refer nonpatent literature 1). The present inventors use organic carbon detection type size exclusion chromatography (LC-OCD) to measure the concentration of a polymer having a molecular weight of 10,000 or more in raw water in water treatment, and the concentration is generally 0. It is confirmed to be in the range of ̃1 mg / L.

  Among the polymers of biometabolites, light-transmissive extracellular polymer particles called TEP (Transparent Exopolymer Particles) are obtained by staining the residue remaining on the filter with a dye called Alcian blue and measuring the absorbance. The concentration can be determined (see, for example, Non-Patent Document 2). Moreover, a method of measuring turbidity without using filter paper is also proposed (see, for example, Patent Document 4). These methods apply the property of the cationic dye, Alcian blue, to be bonded to the carboxyl group of TEP, and are quantified using xanthan gum as a standard substance. Therefore, there is a problem that it can not be applied to neutral sugars having no carboxyl group.

Patent No. 4577122 Patent No. 5407994 Japanese Examined Patent Publication 2-15243 International Publication No. 2014/002748

High sensitivity phenol-sulfuric acid method, Takeuchi et al., Obidaikenho, 22, 103-107 (2001) Regarding analysis of TEP, TORAY TECHNO technical data, No. 1307

  The present invention has been made in view of the above-mentioned conventional situation, and a method of accurately measuring the concentration of a small amount of polymer present in water contaminating a functional material such as a selective permeable membrane or resin in water treatment An object of the present invention is to provide a water treatment method in which the amount of addition of a coagulant is controlled based on the measurement results.

As a result of intensive studies to solve the above problems, the inventors of the present invention react flocculation agents that enhance the removal effect of macromolecules of biological metabolite type with macromolecules to form aggregates and change in turbidity. It was found that the concentration of the polymer can be determined by measuring.
The present invention has been achieved based on such findings, and the gist of the present invention is as follows.

[1] A method for measuring the concentration of a polymer in water, which comprises adding a melamine resin or a phenolic resin to a sample water to be measured and reacting with the polymer in the sample water, and then causing turbidity of the sample water Measuring the concentration and determining the concentration of the polymer based on the measured value of the turbidity.

[2] In [1], a buffer solution is mixed with the sample water to perform pH adjustment, and the turbidity is then measured.

[3] The method according to [1] or [2], wherein the melamine resin forms colloidal particles.

[4] [1] or [2], wherein the phenolic resin is a resol type phenolic resin obtained by performing a resol secondary reaction with a novolak type phenolic resin, and the polymer concentration in water How to measure

[5] In any one of [1] to [4], a process of removing an anion component and / or a turbidity component from the sample water is performed before the addition of the melamine resin or the phenolic resin. Method for measuring the concentration of macromolecules in water.

[6] In any one of [1] to [5], the sample water is treated with a filtration membrane to determine changes in turbidity before and after the treatment,
A method for measuring the concentration of a polymer in water, comprising determining the concentration of the polymer based on the measured value of the turbidity of the sample water after the addition of the melamine resin or the phenolic resin and the change in the turbidity.

[7] In any one of [1] to [6], the concentration of humic substance or protein in the sample water is measured, and the turbidity due to the humic substance or protein is determined from the concentration, and the melamine resin or phenolic resin What is claimed is: 1. A method of measuring the concentration of a polymer in water, comprising determining the concentration of the polymer based on the measured value of the turbidity of sample water after the addition and the turbidity due to the humic substance or protein.

[8] The method according to any one of [1] to [7], wherein the polymer is an acidic polysaccharide or a neutral polysaccharide having a molecular weight of 10,000 or more.

[9] A water treatment method including the step of adding a flocculant to raw water and carrying out a coagulation treatment, wherein the flocculant is obtained based on the polymer concentration of the raw water obtained by the method of any of [1] to [8]. Water treatment method characterized by controlling the addition amount of

[10] The water treatment method according to [9], further including the step of treating the coagulated water with a permeable membrane or a functional resin.

  According to the present invention, it is possible to accurately measure the concentration of a polymer of biological metabolite type, particularly polysaccharide, contained in a trace amount in raw water of water treatment, and based on this result, a selectively permeable membrane or resin Etc., and take measures such as coagulation treatment, adsorption treatment, and drug addition treatment to remove and disperse polymers in the raw water, and control these treatment conditions. As a result, it is possible to perform stable and efficient water treatment while reducing contamination of functional materials.

It is a graph which shows the relationship between the guar gum density | concentration of the sample water in Example 1, and turbidity. It is a graph which shows the relationship of the guar gum density | concentration and turbidity of sample water in Example 2-1. It is a graph which shows the relationship between the xanthan gum density | concentration of sample water and turbidity in Example 2-2. It is a graph which shows the relationship between dextran concentration of sample water and turbidity in Example 2-3. It is a graph which shows the relationship of the dextran density | concentration and turbidity of sample water in Example 2-4. It is a graph which shows the relationship between the Canadian fulvo concentration of the sample water and turbidity in Example 2-5. It is a graph which shows the relationship between dextran concentration of sample water and turbidity in Example 2-6. It is a graph which shows the relationship of the dextran density | concentration of the sample water in Example 2-6, and the turbidity except the turbidity of canadian fulbo. It is a graph which shows the relationship of the bovine serum albumin (BSA) density | concentration and turbidity in Example 2-8.

  Hereinafter, embodiments of the method for measuring the concentration of a polymer in water and the method for treating water according to the present invention will be described in detail.

  In the present invention, “raw water” refers to water treated with a functional material such as a selective permeable membrane or a resin by being pretreated or added with a drug as needed. The water supplied to the functional material after pretreatment, drug treatment, if necessary, is referred to as "feed water".

[Sample water]
The above-mentioned raw water is mentioned as sample water used as a measuring object of polymer concentration in a measuring method of polymer concentration in water of the present invention.
Raw water is raw water in seawater desalination, production of ultrapure water, industrial water treatment, drainage recovery treatment, etc., and is, for example, seawater, lake water, river water, groundwater, drainage, biologically treated water.
In the present invention, the raw water may be pretreated and treated with a drug as needed, and the supplied water supplied to the functional material may be treated.

  The present invention is particularly effective for measuring the concentration of, for example, about 0.1 to 1 mg / L of a polymer of biological metabolite type, particularly polysaccharide, which is contained in a trace amount at a concentration of 1 mg / L or less in sample water.

  According to the present invention, the concentration of various polymers, preferably polysaccharides, particularly preferably acid polysaccharides and neutral polysaccharides in the sample water can be accurately measured. In the case of a neutral polysaccharide, if the molecular weight of the polymer to be measured is too low, the formation of aggregates may not be sufficiently reflected in the turbidity measurement value. From this point of view, when the polymer to be measured is a neutral polysaccharide, the molecular weight is preferably 10,000 or more.

[Aggregation drug]
In the present invention, a melamine resin or a phenolic resin (hereinafter, these may be referred to as "flocculating agent") is added to the sample water in order to react with the polymer component in the sample water to generate a turbidity component. .

  As a phenol resin, a novolak-type phenol resin, a resol type phenol resin, and polyvinyl phenol can be mentioned, for example. A novolac type phenol resin obtained by reacting phenols and aldehydes in the presence of an acid catalyst is used as an alkaline solution, and aldehydes are added thereto to perform a secondary reaction of resol type in the presence of the alkali catalyst. The reaction product obtained may be used. By using this reaction product, the polymer in the sample water can be more effectively aggregated and reflected in the turbidity even at a low concentration, which is preferable.

  Novolak-type phenolic resin is subjected to polycondensation reaction of phenols and aldehydes in the presence of an acidic catalyst in a reaction kettle according to a conventional method, followed by dehydration and removal of unreacted phenol under normal pressure and reduced pressure. Manufactured.

  Examples of phenols include phenol, cresols of o, m and p, ethyl phenols of o, m and p, alkylphenols such as xylenol isomers, and polyaromatic ring phenols such as α and β naphthols. And bisphenol A, bisphenol F, bisphenol S, pyrogallol, resorcin, polyhydric phenols such as catechol, hydroquinone and the like, but it is not limited thereto. These phenols may be used alone or in combination of two or more. Among these, practical substances are phenol, cresols, xylenols and catechol.

  Aldehydes include, but are not limited to, formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, salicylaldehyde, glyoxal and the like. These aldehydes may be used alone or in combination of two or more. Among these, practical substances are formaldehyde and paraformaldehyde.

  As a solvent which dissolves novolac type phenol resin and doubles as an alkali catalyst of resol type secondary reaction, hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide and alkaline earth metals The aqueous solution containing 1 type, or 2 or more types of is mentioned.

  The weight average molecular weight of the phenolic resin is preferably about 1,000 to 1,000,000 from the viewpoint of handleability and aggregation effect. Here, the weight average molecular weight is a value measured by the GPC method (gel permeation chromatography method) and calculated using a calibration curve with standard polystyrene. The same applies to the weight average molecular weight of the melamine resin described later.

  As the melamine resin, for example, alkylol melamine which is a condensation reaction product of melamine and aldehydes, acid colloid of melamine resin obtained by adding an acid to alkylol melamine, acid obtained by alkyl etherifying alkylol melamine. And acid colloids of melamine resins obtained by adding them. Among these, by using an acid colloid of a melamine resin, the polymer in the sample water can be more effectively aggregated and reflected in the turbidity even at a low concentration, which is preferable.

  Examples of aldehydes used in the condensation reaction with melamine include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde and the like, with formaldehyde and paraformaldehyde being particularly preferable in terms of reaction efficiency and handleability.

  The weight average molecular weight of the melamine resin is preferably about 1,000 to 10,000,000 in terms of handleability and aggregation effect.

  The addition amount of these aggregating agents to the sample water may be any amount sufficient to react with the total amount of the polymer in the sample water to form an aggregate, and the type of the polymer contained in the sample water Although depending on the concentration and the concentration, generally, when the above-mentioned raw water and feed water are used as the sample water, it is preferable to set the addition amount of the aggregating agent to about 0.1 to 10 mg / L.

[Preprocessing etc]
In the present invention, the aggregating agent is reacted with the polymer component in the sample water to generate an aggregate, and the turbidity is measured. Therefore, when the sample water contains a turbid substance (turbidity component), Suspended matter affects the result of measurement of turbidity, and it may not be possible to accurately measure turbidity due to polymer aggregates. Therefore, when the suspended matter is contained in the sample water, it is desirable to remove the turbidity component in advance by membrane separation, filtration, centrifugation or the like. For example, when filtered through a microfiltration membrane having a pore size of 0.45 μm, suspended solids (SS) can be removed with little removal of polysaccharides.

  If the raw water contains an anionic substance such as humic substance, this may affect the measurement of the turbidity. Therefore, after the pretreatment to remove the anion component with an anion exchange resin etc. Addition and measurement of turbidity. In this case, although the acid polysaccharide in the sample water may be reduced, most of the substances to be adsorbed are humic substances which are anionic components. Anionic substances and polysaccharides can also be separated using an ultrafiltration membrane. In this case, polysaccharides are concentrated on the primary side of the membrane.

  Alternatively, the turbidity may be measured after mixing a buffer solution (buffer solution) for pH adjustment. That is, the reaction of the melamine resin with the polymer in the sample water is preferably performed in the range of pH 3 to 6 in terms of reactivity, and the reaction of the phenolic resin with the polymer in the sample water is pH 5 to 8 Since it is preferable to carry out in the range of (1), it is preferable to adjust the pH to the above-mentioned suitable pH by adding a buffer solution as necessary. A phosphoric acid solution or an acetic acid solution can be used as the buffer solution.

[Measurement of turbidity]
A common turbidimeter can be used for the measurement of the turbidity after making it react by adding an aggregating agent to sample water.
The turbidity may be measured immediately after adding an aggregating agent to sample water and stirring and mixing, or may be measured after standing for a predetermined time, but depending on the type of polymer in the sample water, aggregation may occur. Immediately after the addition of the drug, the formed aggregates may not be sufficiently reflected in the turbidity measurement value, and an accurate measurement value may not be obtained. In this case, it is preferable to perform the measurement after standing for about 0.5 to 5 hours.

  In order to remove the influence of humic substances contained in the sample water, the sample water is treated with a microfiltration membrane or ultrafiltration membrane, etc., and the turbidity change caused by the humic substances from the change in the turbidity before and after the treatment The concentration may be determined based on a value obtained by subtracting the turbidity caused by humic substances from the measurement value of the turbidity of the sample water to which the aggregation agent is added, and determining the concentration.

  In addition, the concentration of humic substances and proteins contained in the sample water is separately measured, the turbidity caused by these substances is detected from the measured concentration, and detection is performed from the measured value of the turbidity of the sample water to which the aggregation drug is added. Based on the value obtained by subtracting the turbidity, the concentration of the polymer in the sample water may be determined. The concentrations of humic substances and proteins can be determined, for example, by measuring a three-dimensional fluorescence spectrum.

[Water treatment]
According to the method for measuring the polymer concentration in water of the present invention, it is possible to accurately measure the concentration of a polymer of a biological metabolite type, particularly polysaccharide, contained in a trace amount in raw water or water for water treatment. Then, based on the measured polymer concentration, it is possible to grasp the contamination to the functional material such as the selective permeable membrane and the resin, and carry out aggregation treatment, adsorption treatment, and drug addition to remove or disperse the polymer in the raw water. By taking measures such as treatment and controlling these treatment conditions, contamination of functional materials such as selective permeable membranes and resins can be reduced, and membrane separation process and resin treatment process can be stable and efficient over a long period of time It becomes possible to drive.
In particular, by controlling the addition amount of the flocculant added to the raw water based on the measurement result of the polymer concentration in the raw water or the feed water determined according to the present invention, it is possible to prevent excess or deficiency of the flocculant It is possible to carry out aggregation treatment and obtain aggregation treated water of good water quality.

  The present invention will be more specifically described by way of the following examples.

Example 1
First, the following first to third solutions were prepared.
First solution (flocculating agent): 0.36 wt% phenolic resin sodium hydroxide solution (pH 11.8). Formaldehyde is added to an alkaline solution of a novolak-type phenolic resin obtained by polycondensation of phenol and formaldehyde as a phenolic resin in the presence of an acid catalyst, and a secondary reaction of resol type is performed in the presence of the alkaline catalyst. The reaction product (weight average molecular weight 10,000) obtained by carrying out was used.
Second solution (buffer): 20 mM phosphate buffer (pH 6.7).
Third solution (polymer solution (sample water)): Gua gum ("Guacol F50", manufactured by Sanei Pharmaceutical Co., Ltd., molecular weight 1,000,000 or more, LC-OCD converted to dextran) at a concentration of 0.1, 0.2, 0.5, Or guar gum aqueous solution dissolved in pure water so as to be 1 mg / L.

  The turbidity of the mixture obtained by stirring and mixing 10 mL of the first solution, 10 mL of the second solution, and 10 μL of the third solution was measured. A turbidity meter (2100Q, manufactured by HACH) was used for the measurement of the turbidity. After the mixture was allowed to stand for 1 hour, the turbidity was measured again.

  In addition, turbidity was measured using pure water as a sample. The value which deducted the turbidity of pure water as a blank from the turbidity of a liquid mixture is shown in Drawing 1 for every concentration of polymer solution. As shown in FIG. 1, in the range where the guar gum concentration was 0.5 mg / L or less, a linear relationship was obtained between the concentration and the turbidity immediately after the addition of the aggregating agent and one hour after. Although guar gum is a polysaccharide composed only of neutral sugars, it was confirmed in the present invention that the concentration can be determined based on the turbidity even at a low concentration of 0.5 mg / L or less.

Example 2-1
First, the following first to third solutions were prepared.
First solution (flocculating agent): 0.2 wt% melamine resin in hydrochloric acid solution (pH 1.2). As a melamine resin, a melamine resin (weight average molecular weight 6,600) prepared by adding 0.05 mol of methylolated melamine obtained by reacting 2 mol of formaldehyde to 1 mol of melamine to 100 mL of a 1.35 wt% aqueous hydrochloric acid solution , 000) acid colloid solution was used.
Second solution (buffer): 100 mM acetate buffer (pH 4.85).
Third solution (polymer solution (sample)): Gua gum ("Guacoal F50" manufactured by Sanei Pharmaceutical Co., Ltd., molecular weight 1,000,000 or more, LC-OCD converted to dextran) at a concentration of 0.1, 0.2, 0.5, or An aqueous solution of guar gum dissolved in pure water so as to be 1 mg / L.

  The turbidity of the mixed solution obtained by stirring and mixing 10 mL of the first solution, 10 mL of the second solution, and 20 μL of the third solution was measured. A turbidity meter (2100Q, manufactured by HACH) was used for the measurement of the turbidity. After the mixture was allowed to stand for 1 hour, the turbidity was measured again.

  In addition, turbidity was measured using pure water as a sample. The value which deducted the turbidity of the pure water as a blank from the turbidity of a liquid mixture is shown in Drawing 2 for every concentration of a polymer solution. As shown in FIG. 2, no turbidity appears at a guar gum concentration of 0.1 mg / L, but at 0.2 to 1 mg / L, the concentration and turbidity of the concentration and turbidity immediately after addition of the aggregating agent and one hour after A linear relationship was obtained between them, and it was confirmed that the concentration could be determined based on the turbidity.

Example 2-2
In Example 2-1, a third solution (polymer solution (sample)) was prepared using a solution of xanthan gum ("Bisfect XA" manufactured by Sanei Pharmaceutical Co., Ltd .; molecular weight of 1,000,000 or more, dextran conversion by LC-OCD) at a concentration of 0.1, 0 The measurement was carried out in the same manner except that the aqueous solution of xanthan gum was dissolved in pure water to be 2, 0.5, or 1 mg / L. The results are shown in FIG. As shown in FIG. 3, a linear relationship between concentration and turbidity was obtained immediately after the addition of the agglutinating agent, at a xanthan gum concentration of 0.1 to 1 mg / L. After 1 hour, the turbidity tended to decrease at a concentration of 1 mg / L. By measuring the turbidity immediately after the addition of the aggregating agent, it was confirmed that the concentration can be determined based on the turbidity in the range of a xanthan gum concentration of 0.1 to 1 mg / L.

Example 2-3
In Example 2-1, the third solution (polymer solution (sample)) has a concentration of 0.1, 0.2, 0.5, or 1 mg / L for dextran (molecular weight 66700 manufactured by SIGMA-ALDRICH). The measurement was carried out in the same manner except that the aqueous dextran solution was dissolved in pure water as described above. The results are shown in FIG. As shown in FIG. 4, in the dextran concentration range of 0.1 to 1 mg / L, the sensitivity was slightly low immediately after the addition of the agglutination agent, but after 1 hour, a remarkable linear relationship between concentration and turbidity was gotten. It has been confirmed that the concentration can be determined based on the turbidity even with a neutral polysaccharide and a polymer having a molecular weight of several tens of thousands.

Example 2-4
In Example 2-1, the third solution (polymer solution (sample)) has a concentration of 0.1, 0.2, 0.5, or 1 mg / L for dextran (molecular weight 9890 manufactured by SIGMA-ALDRICH). The measurement was carried out in the same manner except that the aqueous dextran solution was dissolved in pure water as described above. The results are shown in FIG. As shown in FIG. 5, the sensitivity was low immediately after the addition of the aggregating agent and after one hour. When detecting neutral polysaccharides, those having a molecular weight of 10,000 or more are preferably assumed to be detection targets.

Example 2-5
In Example 2-1, the third solution (polymer solution (sample)) has a concentration of 0.1, 0.2, 0.5, 1, or 2 mg / L of Canadian fulbo (manufactured by Pyi Bio). The measurement was conducted in the same manner except that the aqueous solution of Canadian fulvo was dissolved in pure water as described above. The results are shown in FIG. As shown in FIG. 6, it can be confirmed that canadian fluvo affects the turbidity immediately after the addition of the aggregating agent at 0.5 mg / L or more and after 1 hour at 0.1 mg / L or more.

Example 2-6
In Example 2-1, the third solution (polymer solution (sample)) has a concentration of 0.1, 0.2, 0.5, or 1 mg / L for dextran (molecular weight 66700 manufactured by SIGMA-ALDRICH). The measurement was carried out in the same manner as described above except that it was dissolved in pure water, and Canadian fulvo was further added to a concentration of 2 mg / L. The results are shown in FIG. As shown in FIG. 7, the turbidity was high even in the low concentration region due to the influence of canadian fulvo both immediately after the addition of the agglutinating agent and after one hour.

  FIG. 8 shows the result of subtracting the turbidity of an aqueous solution of Canadian fulvic at a concentration of 2 mg / L in Example 2-5 from the turbidity shown in FIG. 7. As shown in FIG. 8, due to the presence of canadian fulvo, which is a component that forms turbidity, the turbidity tends to rise immediately after the addition of the aggregating agent. Although the difference between immediately after addition of the aggregating agent and after 1 hour is smaller compared to Example 2-3, in the region of dextran concentration 0.1 to 1 mg / L, the linear relationship between concentration and turbidity is It was confirmed that the concentration was obtained based on the turbidity obtained.

Example 2-7
In Example 2-5, the Canadian fulvo concentration of the polymer solution was determined by measuring a three-dimensional fluorescence spectrum. The relationship between the average value of the fluorescence intensity measured at intervals of 5 nm and the concentration in the excitation wavelength range of 290 to 340 nm and the fluorescence wavelength of 410 to 455 nm is as follows, even if the concentration of the canadian fulvo of the sample water is unknown The concentration of canadian fluvo can be determined from the fluorescence intensity, and by combining the results of Example 2-5, the influence of canadian fluvo on turbidity can be determined, and the concentration of polysaccharide can be determined.
Also, as a method of excluding the influence of canadian fluvo, the sample water is treated with an ultrafiltration membrane and the effect of only canadian flubo on the turbidity is examined, and the results obtained. Can also be used as a blank.

Example 2-8
In Example 2-1, the third solution (polymer solution (sample)) was diluted with bovine serum albumin (BSA fraction V, manufactured by Wako Pure Chemical Industries, Ltd.) at a concentration of 0.1, 0.2, 0.5, or 1 mg / mg. The measurement was performed in the same manner as in the above except that the BSA aqueous solution was dissolved in pure water so as to be L. The results are shown in FIG. As shown in FIG. 9, a linear relationship between concentration and turbidity was obtained in the range of 0.1 to 1 mg / L one hour after the addition of the aggregating agent. The sensitivity was about half of that of dextran of the same molecular weight, but it was confirmed that the concentration was determined based on the turbidity. Immediately after the addition of the aggregating agent, the turbidity tends to increase as the concentration increases, but the sensitivity is not high.

Example 2-9
In Example 2-8, the BSA concentration of the polymer solution was determined by measuring a three-dimensional fluorescence spectrum. The relationship between the average value of the fluorescence intensity measured at intervals of 5 nm and the concentration in the range of excitation wavelength 260 to 290 nm and fluorescence wavelength 325 to 380 nm is as follows, and the BSA concentration of the sample water is unknown. Even in the case of coexistence, the BSA concentration is determined from the fluorescence intensity, and the results of Example 2-8 can be combined to determine the influence of BSA on the turbidity, and the concentration of polysaccharide can be determined.
BSA concentration = 3.44 x fluorescence intensity

Comparative Example 1
According to the method described in Non-Patent Document 1 (High-sensitivity phenol-sulfuric acid method, Takeuchi et al., Bandaiken, 22, 103-107 (2001)), measurement of the concentration of guar gum was attempted by the phenolic sulfuric acid method. The results are shown in Table 1. At a concentration of 1 mg / L or less, no significant difference was observed in the absorbance (ABS) at a wavelength of 490 nm, confirming that the concentration could not be measured.

  Table 2 shows the relationship between the concentration of glucose often used as a standard substance of the phenol sulfuric acid method and the absorbance (ABS) at a wavelength of 490 nm. Although a linear relationship is established between the concentrations of 10 mg / L and 100 mg / L, it was confirmed that there was no significant difference in absorbance at 1 mg / L or less, and the concentration could not be measured.

Claims (10)

A method for measuring the concentration of a polymer in water, which is a melamine resin or a phenolic resin as an aggregating agent (excluding an inorganic coagulant) for generating an aggregate as a turbid component in sample water to be measured Is added to react with the polymer in the sample water to form an aggregate as a turbid component, and the turbidity of the sample water is measured, and the polymer concentration is determined based on the measured value of the turbidity. Ask for
Among the polymers in the sample water, a polymer of a biological metabolite type is contained at a concentration of 1 mg / L or less .   The method according to claim 1, wherein the sample water is mixed with a buffer solution to perform pH adjustment, and then the turbidity is measured. A method for measuring the concentration of a polymer in water, which comprises adding a melamine resin or a phenolic resin to a sample water to be measured and reacting with the polymer in the sample water, and then measuring the turbidity of the sample water And determining the concentration of the polymer based on the measured value of the turbidity.
Method of measuring the polymer concentration in the water before Symbol melamine resin is characterized in that to form colloidal particles.   The method for measuring the polymer concentration in water according to claim 1 or 2, wherein the phenol resin is a resol type phenol resin obtained by performing a resol type secondary reaction on a novolak type phenol resin. A method for measuring the concentration of a polymer in water, which comprises adding a melamine resin or a phenolic resin to a sample water to be measured and reacting with the polymer in the sample water, and then measuring the turbidity of the sample water And determining the concentration of the polymer based on the measured value of the turbidity.
Prior to the addition of pre-Symbol melamine resin or phenolic resin, the measuring method of the polymer concentration in water, which comprises carrying out a process of removing an anion component and / or turbidity component from the sample water. A method for measuring the concentration of a polymer in water, which comprises adding a melamine resin or a phenolic resin to a sample water to be measured and reacting with the polymer in the sample water, and then measuring the turbidity of the sample water And determining the concentration of the polymer based on the measured value of the turbidity.
The pre-Symbol sample water by filtration membrane process, determine the change in the before and after treatment turbidity,
A method for measuring the concentration of a polymer in water, comprising determining the concentration of the polymer based on the measured value of the turbidity of the sample water after the addition of the melamine resin or the phenolic resin and the change in the turbidity. A method for measuring the concentration of a polymer in water, which comprises adding a melamine resin or a phenolic resin to a sample water to be measured and reacting with the polymer in the sample water, and then measuring the turbidity of the sample water And determining the concentration of the polymer based on the measured value of the turbidity.
The concentration of the humic substances or protein before Symbol sample water is measured, determine the turbidity by humic substances or proteins from the concentration,
Measurement of polymer concentration in water characterized by determining polymer concentration based on the measurement value of the turbidity of sample water after addition of the melamine resin or phenolic resin and the turbidity caused by the humic substance or protein Method.   The method according to any one of claims 1 to 7, wherein the polymer is an acidic polysaccharide or a neutral polysaccharide having a molecular weight of 10,000 or more.   A water treatment method comprising the step of adding a flocculant to raw water and carrying out coagulation treatment, wherein the addition amount of the flocculant is controlled based on the polymer concentration of the raw water obtained by the method according to any one of claims 1 to 8. Water treatment method characterized in that.   The water treatment method according to claim 9, further comprising the step of treating the coagulated water with a permeable membrane or a functional resin.

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