JP4658873B2 - Aggregation treatment agent and method for stabilizing aqueous solution of aggregation treatment agent - Google Patents

Description

The present invention relates to a flocculating agent having a stable solution, and more specifically, a polymer flocculant, a reducing agent, and an amount that makes the solution pH 6 or less when the polymer flocculant is dissolved in 0.1% by mass or more. The present invention relates to an aggregating treatment agent in which a solution is stable by combining three components of acidic substances. Further, when dissolving the aggregating agent, after treating with a reducing agent and an acidic substance in dissolved water, the polymer aggregating agent is dissolved, or the polymer aggregating agent, the reducing agent and the acidic substance are dissolved at the same time. It also relates to a method for stabilizing a molecular flocculant solution.

When the powdery polymer flocculant is used for sewage treatment, human waste treatment, industrial wastewater treatment, and other wastewater treatment, it is dissolved using dissolution water in a dissolution tank, and is usually made into a 0.1 to 0.3% concentration solution. This is added to the treatment tank. Normally, industrial water, river water, treated water (reclaimed water after water treatment), etc. are used as dissolved water because of cost, but the properties of the dissolved liquid are the quality of the dissolved water, especially impurities such as residual chlorine and electrolytes. Depending on the type and concentration, dissociation of the ionic functional group is inhibited, resulting in a decrease in viscosity and deterioration over time, which affects the aggregation performance. In wastewater treatment facilities, treated water is often used as dissolved water, but the treated water often contains residual chlorine and metal salts resulting from chlorine sterilization. For this reason, not only treated water but also a solution with reduced viscosity may be obtained depending on the concentration of residual chlorine, electrolyte and other impurities in the dissolved water, and a solution having no viscosity may be obtained. The agglomeration performance is greatly reduced. Also, in many cases, after preparation of the solution, it is affected by impurities, pH, etc., resulting in a decrease in molecular weight due to alteration or decomposition of the polymer flocculant. There is also a problem in that the viscosity of the liquid decreases. For this reason, there is an inconvenience that a polymer flocculant solution cannot be prepared and must be used as soon as possible after preparation.

As described above, the polymer flocculant solution has a problem of a decrease in viscosity when dissolving the polymer flocculant and a decrease in viscosity over time during storage after preparation of the solution. As a method for suppressing the decrease in viscosity over time due to the latter hydrolysis, a method has been proposed in which an acid is added to a solution to make an aqueous solution an acidic region (Patent Documents 1 and 2). However, these methods cannot cope with a decrease in viscosity at the time of dissolution.
JP 54-69582 A JP-A-5-255565

As described above, the properties of the polymer flocculant solution greatly depend on the properties of the dissolved water, and a low-viscosity solution can be obtained by residual chlorine, electrolytes and other impurities contained in the dissolved water. There is a problem that the viscosity decreases. For example, in the case of water sterilized with hypochlorite and containing a lot of residual chlorine, the viscosity decreases particularly during dissolution, and depending on the residual chlorine concentration, the solution may not exhibit any viscosity. . This decrease in viscosity at the time of dissolution is caused by a decrease in the reactivity and decomposition of the polymer flocculant due to residual chlorine and impurity ions. An object of the present invention is to solve these problems and to provide a polymer flocculant that exhibits normal and stable flocculation performance and a method for stabilizing a solution.

As a result of intensive studies to solve the above problems, the present inventors have determined that the solution pH when the polymer flocculant, the reducing agent, and the polymer flocculant are dissolved in 0.1% by mass or more is 6%. When a coagulation treatment agent consisting of a combination of the three components of acidic substances in the following amount is dissolved, the viscosity decrease at the time of dissolution of the polymer coagulant is suppressed, and further the viscosity decrease over time during storage is suppressed. It was discovered that a stable aqueous solution was obtained and the present invention was reached.

The aggregating agent is preferably a powdery or granular mixture comprising a polymer aggregating agent, a reducing agent and an acidic substance.

In the present invention, when the aggregating agent is dissolved in dissolved water to form an aqueous solution, the solution pH when the reducing agent and the polymer aggregating agent are dissolved in 0.1% by mass or more in dissolved water is 6 It is characterized in that a stable aggregating agent aqueous solution can be obtained by dissolving the polymer flocculant after dissolving the amount of acidic substance to be described below, or by dissolving the polymer flocculant, the reducing agent and the acidic substance at the same time. The present invention also relates to a method for stabilizing an aggregating agent aqueous solution.

The polymer flocculant aqueous solution is affected by the residual chlorine, electrolyte, and other impurities contained in the dissolved water, and the polymer flocculant in the solution undergoes modification such as hydrolysis, resulting in a decrease in viscosity during dissolution and a decrease in viscosity over time. Cause normal agglomeration performance. In order to solve this problem, the present invention provides the following method. That is, the present invention comprises a combination of a polymer flocculant, a reducing agent, and three components of an acidic substance in an amount that makes the solution pH 6 or less when the polymer flocculant is dissolved in 0.1% by mass or more. It is an aggregating agent.

The aggregating agent of the present invention is a powdery substance comprising an acidic substance in an amount that makes the solution pH 6 or less when the polymer flocculant, the reducing agent and the polymer flocculant are dissolved in 0.1% by mass or more. It can be a granular mixture. Since the reducing agent has a property of neutralizing and reducing residual chlorine in the dissolved water, and the acid suppresses hydrolysis of the polymer flocculant, the stability of the aqueous solution can be improved.

In addition, when the aggregating agent of the present invention is dissolved in dissolved water to form an aqueous solution, the solution pH when the reducing agent and the polymer aggregating agent are dissolved in 0.1% by mass or more in dissolved water is 6 or less. After the amount of the acidic substance to be dissolved is dissolved, the polymer flocculant is dissolved, or the polymer flocculant, the reducing agent, and the acidic substance are dissolved simultaneously to stabilize the aqueous flocculating agent solution. Can do.

The reducing agent used in the present invention is as follows. That is, thiosulfate, sulfite, bisulfite, hypophosphite, L-ascorbic acid or a salt thereof, or hydrazines. One or a combination of two or more selected from these. Since these reducing agents have the property of neutralizing and reducing residual chlorine in the dissolved water, the amount of water that is usually 5 to 500 pppm is added to the dissolved water, although it varies depending on the properties of the dissolved water, particularly the residual chlorine concentration. To exert its effect. Of these, thiosulfate is particularly preferred because it has the property of neutralizing and reducing residual chlorine in dissolved water and further incorporating metals. When the polymer flocculant, the reducing agent, and the acidic substance are sequentially added and dissolved as the addition amount of these reducing agents, the amount is 0.0005 to 0.01% by mass with respect to the dissolved water, preferably 0.001 to 0.00. 005% by mass. Moreover, when preparing a product as a powdery or granular mixture, it is 0.5-5 mass% with respect to a polymer flocculent, Preferably it is 0.5-2 mass%.

Moreover, an acidic substance is an acidic substance of the quantity which makes the solution pH 6 or less at the time of melt | dissolving a polymer flocculent in 0.1 mass% or more. Examples of such acidic substances include hydrochloric acid, sulfuric acid, acetic acid, inorganic or organic acids,
Sulfamic acid, citric acid, fumaric acid, succinic acid, adipic acid and the like. Further, the flocculating agent of the present invention can be made into a powdery or granular product form containing three components of a polymer flocculating agent, an acidic substance and a reducing agent. In that case, a solid inorganic or organic acid is preferable, and sulfamic acid, citric acid, fumaric acid, succinic acid, adipic acid and the like are preferable. The amount of these acidic substances to be added is 0.001 to 0.01% by mass with respect to the dissolved water, preferably 0.001 to 0.005%, when a polymer flocculant, a reducing agent, and an acidic substance are sequentially added and dissolved. 005% by mass. Moreover, when preparing a product as a powdery or granular mixture, it is 0.1-10 mass% with respect to a polymer flocculent, Preferably it is 0.5-5 mass%.

The polymer flocculant used in the present invention may be any of a cationic polymer flocculant, an anionic polymer flocculant, and an amphoteric polymer flocculant. Examples of cationic polymer flocculants include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, homopolymers of quaternary salts or tertiary salts thereof, and copolymers thereof with acrylamide or methacrylamide. Products, polyacrylamide or polymethacrylamide Hoffman degradation products, polyamidine, and the like. Anionic polymer flocculants include sodium acrylate polymer, copolymer of sodium acrylate or sodium methacrylate and acrylamide or methacrylamide, partial hydrolyzate of acrylamide polymer or methacrylamide polymer, acrylamide or methacrylic acid. Examples include, but are not limited to, terpolymers of amide and sodium acrylate or sodium methacrylate and sodium 2-acrylamido-2-methylpropanesulfonate. Amphoteric polymer flocculants include anionic monomer and cationic monomer copolymer, anionic monomer, cationic monomer and nonionic monomer copolymer, or anionic monomer and cationic monomer copolymer Mannich. Examples include, but are not limited to, denatured products or Hoffman degradation products.

The dissolved water is usually all water used as dissolved water, and specifically includes treated water treated with waste water, industrial water, river water, tap water, and the like. It is particularly effective for treated water containing residual chlorine that has been sterilized with chlorine.

EXAMPLES The present invention will be described more specifically with reference to the following examples and comparative examples. However, the present invention is not limited to these examples.

Treated water in a sewage treatment plant (residual chlorine: 1.8 mg / l, evaporation residue: 980 mg / l) was used as dissolved water, and a cationic polymer flocculant (acryloyloxyethyltrimethylammonium chloride 60 mol%) in 500 ml thereof. 1 g of acrylamide 40 mol% copolymer, molecular weight 7 million) and sodium thiosulfate in mass% listed in Table 1 are added, and dissolution treatment is performed with stirring for 1 hour. Sulfamic acid was added to the resulting solution so as to have the pH described in Table 1. This solution is allowed to stand at room temperature, sampled 5 times in total, immediately after dissolution, 2 hours, 8 hours, 24 hours and 72 hours, and the respective viscosities are measured. The results are shown in Table 1.

(Comparative Example 1) Tap water (residual chlorine: 0.7 mg / l, evaporation residue: 122 mg / l) was used as dissolved water, and 1 g of a cationic polymer flocculant similar to that used in the example was added to 500 ml thereof. The dissolution treatment is performed for 1 hour under stirring. The pH of the resulting solution is 6.5. This solution is allowed to stand at room temperature, sampled 5 times in total, immediately after dissolution, 2 hours, 8 hours, 24 hours, and 72 hours, and the respective viscosities are measured. The results are shown in Table 1.

(Comparative Example 2) Using treated water (residual chlorine: 1.8 mg / l, evaporation residue: 980 mg / l) in the same sewage treatment plant as used in Examples as dissolved water, 500 ml thereof was compared with Comparative Example 1 1 g of the same cationic polymer flocculant is added, and dissolution treatment is performed for 1 hour with stirring. The pH of the resulting solution is 6.6. This solution is allowed to stand at room temperature, sampled 5 times in total, immediately after dissolution, 2 hours, 8 hours, 24 hours, and 72 hours, and the respective viscosities are measured. The results are shown in Table 1.

(Comparative Example 3) Treated water in the sewage treatment plant A (residual chlorine: 1.8 mg / l, evaporation residue: 980 mg / l) was used as dissolved water, and 500 ml of the same cationic polymer agglomerates as in Comparative Example 1 1 g of the agent and sodium thiosulfate in mass% described in Table 1 are added, and dissolution treatment is performed for 1 hour with stirring. The pH of the resulting solution is 6.4. This solution is allowed to stand at room temperature, sampled 5 times in total, immediately after dissolution, 2 hours, 8 hours, 24 hours, and 72 hours, and the respective viscosities are measured. The results are shown in Table 1.

From the table, it can be seen that Comparative Example 1 shows a high viscosity immediately after dissolution, but then gradually decreases in viscosity over time. In Comparative Example 2, it can be seen that the initial viscosity is extremely low and the viscosity decrease with time is large. Furthermore, in Comparative Example 3, it can be seen that the initial viscosity is low and the viscosity decrease with time is large. In contrast, it can be seen that the aggregation treatment agent of the present invention has a small decrease in viscosity even after 72 hours.

ＲＣｌ；残留塩素量、ＳＴＳ；チオ硫酸ナトリウム添加量、ＳＡ；スルファミン酸、ｐＨ；調製後ｐＨ、 (Table 1) Change in viscosity of solution over time

RCl: amount of residual chlorine, STS: amount of sodium thiosulfate added, SA: sulfamic acid, pH: pH after preparation,

(Preparation of Aggregation Treatment Agent Containing Powder and Solution Storage Test) A powdery aggregation treatment agent was prepared by blending each component in mass% described in Table 2. In addition, these powdery flocculating agents were dissolved in the same manner as in Example 1 using treated water in sewage treatment plant A (residual chlorine: 1.8 mg / l, evaporation residue: 980 mg / l) to 0.2% by mass. It melt | dissolved and measured the solution viscosity for every elapsed time. Table 2 shows the polymer flocculant composition and blending ratio, and Table 3 shows the results of the solution storage test.

(Comparative Example 4) A similar solution storage test was conducted for Comparative Sample-1 and Comparative Sample-2. The results are shown in Table 3.

高分子凝集剤化学組成；モル％、配合比；質量％ (Table 2)

Polymer flocculant chemical composition; mol%, compounding ratio; mass%

(Table 3)

Claims (4)

As a polymer flocculant , dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate or a homopolymer of quaternary salt or tertiary salt thereof, or a copolymer of them with acrylamide or methacrylamide, reduction As the agent , at least one selected from thiosulfate, sulfite, bisulfite, and L-ascorbic acid and the polymer flocculant dissolved in 0.1% by mass or more have a pH of 6 or less. An aggregating treatment agent comprising a combination of at least one ternary component selected from sulfamic acid and succinic acid as the amount of acidic substance. The aggregating agent according to claim 1, wherein the aggregating agent is a powdery or granular mixture comprising a polymer aggregating agent, a reducing agent and an acidic substance. When the aggregating agent according to claim 1 is dissolved in dissolved water to obtain an aqueous solution, the solution pH when the reducing agent and the polymer aggregating agent are dissolved in dissolved water at 0.1% by mass or more is 6 An aqueous flocculating agent solution comprising: dissolving the polymer flocculant after dissolving an amount of the acidic substance to be described below; or dissolving the polymer flocculant, the reducing agent, and the acidic substance simultaneously. Stabilization method. The method for stabilizing an aggregating agent aqueous solution according to claim 3 , wherein the dissolved water is at least one selected from industrial water, river water, and treated water after wastewater treatment.