JPH1028808A - Special solid fine powdery flocculant composition and water treatment method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a special solid fine powdery flocculant compsn. added to waste water to be treated to flocculate a suspended pollutant within a short time by stirring or dispersing action to obtain supernatant water excellent in clarity and a treatment method using said compsn. SOLUTION: The special solid fine powdery flocculant composition having functionality is prepared by a water soluble aluminum salt or iron salt type inorg. flocculant, a self-pH regulator, a polymeric flocculant finer than a usually used one and other essential component in a powdery granule form and is directly added to waste water to be treated alone to complete flocculation under stirring and formed flocs stable in form and excellent in dehydration properties are separated to be excluded out of the system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a special solid fine powdery flocculant composition and a method for treating wastewater using the same.
More specifically, the composition of the present invention in which a specific substance is formed at a predetermined compounding ratio, and the composition is applied to a wastewater to be treated to aggregate pollutant components in a short time to form flocs that can be easily separated. About technology.

[0002]

2. Description of the Related Art Conventionally, as a coagulant generally used for wastewater treatment, an inorganic coagulant represented by a sulfuric acid band, polyaluminum chloride and the like, pH adjustment and, if necessary, a liquid natural or synthetic high coagulant. It is well known that a molecular coagulant is injected and stirred to separate polluted components from the wastewater as flocs. In any case, since the flocculant is handled as an aqueous solution, the addition amount can be maintained relatively accurately even in a small amount. However, on the other hand, the cost of storing and transporting the flocculant is high, and in particular, the polymer flocculant often completely dissolves in the field, and it often poses a problem that the preparation requires a lot of trouble and a long time. Therefore, if a system that takes a considerable amount of time for the treatment as a whole and that ensures the reaction and the residence time satisfactorily is adopted, a high initial cost is required as a facility opening cost, which cannot be said to be preferable.

On the other hand, various studies have been made to improve the complexity of wastewater treatment using such a flocculant, and a method of selecting a conventional flocculant and a flocculant and processing conditions suitable for this method have been studied. In addition, modification of the flocculant itself is also being studied. For example, as a means to increase the coagulation treatment speed or to improve the dewatering property of generated flocs, in addition to the conventional coagulant, diatomaceous earth, clay,
Various improvement measures have been studied and reported, such as a method of adding gypsum, limes, calcium carbonate, and the like, or development of a flocculant composition having a pH adjusting function also intended to improve a wastewater treatment process.

As one example, Japanese Patent Application Laid-Open No. Hei 7-136409
In the patent publication, as a coagulant that can be discharged without the need for neutralization of the treated water, aluminum sulfate, calcium sulfate of a specific number of parts, an alkali metal carbonate as a pH adjuster, and cement as a sedimentation agent for coagulated floc, respectively. In addition, examples of mixed compositions of various types such as zeolite or a cationic flocculant are shown.

The wastewater to be subjected to the coagulation treatment includes not only general factory wastewater but also muddy water from a subway construction site.
It is complicated and diversified, such as drainage for shields in tunnel construction and concrete drainage at ready-mixed concrete sites. In some cases, standard processes cannot be adopted at all, and there are many cases where it is unavoidable to deal with more compact and simple equipment. In terms of aspect, there is a need for a more reliable method that can be easily processed.

[0006]

As described above, according to the conventional processing method, the equipment employed is complicated,
In addition to requiring a considerable installation area for the processing equipment, the operation becomes complicated and the initial cost and running cost must be high.For example, direct treatment tends to be insufficient at civil engineering construction sites, etc. . In addition, with respect to the remedies by various kinds of coagulant compositions which have been published, the present invention is applied to a wide range of wastewater, and not all of them can provide a preferable supernatant water after separation of generated floc. Furthermore,
There are still many difficulties such as improvement in the properties of the generated flocs and easy handling in actual work, and it is still necessary to repeat detailed development studies on the mixed composition or the types and distribution of the constituent components.

In view of the above situation, the present inventors have found that the handling is easy and the initial cost is low. We have intensively studied to develop a special solid fine powdered flocculant composition that can be used as a stable and stable floc. As a result, the present inventors have developed a special solid fine powder type flocculant composition which exerts a flocculating action on a relatively wide range of wastewater in a short time and the formed floc is more stable, compact and has good dewatering properties. The patent application has been completed as Japanese Patent Application No. Hei 8-091629.

That is, the gist of the invention is that a soluble aluminum compound or a soluble iron salt compound, a natural or synthetic polymer flocculant, or the like is used as a flocculant, and an aqueous solution of the flocculant is used at a pH value near neutrality. And alkali metal carbonates and / or cement powders are blended to such an extent that at least two particles selected from the group consisting of alkaline earth metal carbonates, bentonite soil mineral powders, and zeolite powders are added. Kind Code: A1 The present invention relates to a special solid fine powdery flocculant composition characterized by mixing seeds and a wastewater treatment method using the composition.

However, in the water treatment with this composition,
Depending on the target wastewater, the supernatant water after treatment is not always transparent and often accompanied by some turbidity, which is not a favorable condition for the appearance of treated water. It had to be laid or lightly reprocessed.

[0010]

Means for Solving the Problems The inventors of the present invention have continued their studies to solve the above-mentioned problems, and as a result, have found that a coagulant composition containing very little or almost no alkaline earth metal carbonate as an auxiliary additive. With respect to the product, it was found that good supernatant water was obtained, and that the formed floc was more stable, compact, and had good dewatering properties, leading to the present invention.

The subject matter of the present invention is that a soluble aluminum compound or a soluble iron salt compound, a natural or synthetic polymer flocculant, or the like is used as a flocculant, and an aqueous solution of the flocculant is neutral at a pH value. It is characterized by comprising a mixture of alkali metal carbonate and / or cement powder to an extent showing the vicinity, and further blending one selected from bentonite soil mineral powder or zeolite powder. It is a special solid fine powder type flocculant composition.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Among the chemicals constituting the composition of the present invention, there are known chemicals which have already been used as components of coagulants in the field of wastewater treatment. The composition of the present invention requires the formation of a specific composition, and the composition of the present invention has an aggregating action based on the synergistic action of each component, and can be easily realized by a known aggregating agent. It has a very novel effect that could not be obtained.

The first feature of the composition of the present invention is that a conventionally used inorganic flocculant, inorganic salt and polymer flocculant can be simultaneously added to waste water as a flocculant. . That is, the point is that the respective aggregating effects are exhibited without impairing both properties of the aggregating action and the cross-linking action. For this reason, it is particularly important to mix the polymer flocculant in the form of a fine powder as much as possible, whereby the polymer flocculant is blended as an inorganic flocculant, an inorganic salt and a third component in which the fine particles of the polymer coexist. The action time substantially coincides with the inorganic fine particles, and the components are dissolved and dispersed at the time of being added to the wastewater without being isolated, and the aggregation reaction is completed in a very short time.

The second feature of the composition of the present invention is that an inorganic coagulant main component which is acidic in water, such as a soluble aluminum compound or a soluble iron salt compound, is mixed with an alkali metal carbonate and / or cement powder. And the pH of the aqueous solution of the aggregating main agent is maintained near neutrality, and there is no need for special pH adjustment. The reason for this is not clear, but is presumed to be due to a buffering effect due to the coexistence of various components other than the neutralizing action. This eliminates or eliminates the need for a pH adjustment facility by injecting a chemical such as an acid or an alkali, thereby improving both initial cost and running cost.

A third feature of the composition of the present invention is that by blending at least one selected from bentonite-based soil mineral powder or zeolite-based powder, the above-mentioned components serve as nuclei for formed flocs. As a synergistic effect of the respective components, an adsorbing action and a flocculating action can be expected, it is also useful for removing COD which is a dissolved component in the wastewater, and the obtained floc is also stably strong and dewaterability is improved. In particular, an excellent effect is observed in combination with the bentonite soil mineral powder. This effect is a dewatered cake having a simple facility and a low water content even when the floc is separated as a cake and dewatered, and as a result, is extremely useful for protection of the global environment.

The fourth feature of the composition of the present invention is that, as described above, it is possible to carry out simple and reliable wastewater treatment. Not only can it be easily processed and recirculated, it can be used, but also at sites where conventional direct treatment is performed, more compact equipment and more reliable treatment are possible, and the amount of waste finally generated is less than before. It is a point that is much less.

The fine powdery polymer flocculant used in the present invention may be either natural or synthetic, and particularly, a synthetic polymer flocculant is preferably a cationic polymer flocculant. As the cationic synthetic polymer flocculant used in the present invention, any commercially available product can be used. On the other hand, various polysaccharides can be used in the natural system, but a fine powder obtained by freeze-drying or spray-drying an aqueous solution of an acidic polysaccharide polymer mainly containing β-1,3 glucan cultured by microorganisms is particularly preferable. .

It is extremely important for the composition of the present invention that the particle size of the fine powder of the polymer flocculant to be used in the present invention is 80 mesh passes or more, preferably 100 mesh passes or more. For coarser particles, wastewater treatment
When the flocculant of the present invention does not show uniform dissolution rate characteristics, and thus adversely affects the promptness in the flocculation reaction surface and increases the partial tackiness of floc, so that it is difficult to achieve the object of the present invention. There is.

The special solid fine powdery flocculant composition of the present invention can be obtained by simultaneously blending the specific compounds constituting the present invention in powder form and mixing them uniformly. As the blending ratio of the composition, it is necessary to variably correspond to each other, but the basic composition is determined by the blending amount of the soluble aluminum or soluble iron salt compound as the flocculant component and the natural or synthetic polymer flocculant. You. To this, an alkali metal carbonate and / or cement powder as a pH adjuster, and as a third component, one selected from bentonite soil mineral powder or zeolite powder as an essential additive selection material Is what you do.

Assuming that these compositions are the composition weight ratio of the whole composition, the soluble aluminum compound or soluble iron salt compound is 15 to 50% by weight, natural or synthetic, assuming that the composition weight ratio of the whole composition is 100%. 0.5 to 25% by weight of a polymer flocculant, 10 to 40% by weight of alkali metal carbonate and / or cement powder,
One type selected from bentonite soil mineral powder or zeolite powder is uniformly mixed in an amount of 10 to 40% by weight to constitute a composition.

In the above composition, when the content of soluble aluminum or soluble iron salt is 15% by weight or less, the cohesive force is weak,
When the effect of the present invention is hardly exerted, the composition of the flocculant performance is difficult at 50% by weight or more. On the other hand, if the concentration of the polymer coagulant is too low, such as 0.5% by weight or less, the effect of the present invention cannot be obtained because the cohesiveness of the composition itself is sharply reduced.
If the weight% or more, a strong sticky floc can be obtained,
It is not preferable because dehydration property is deteriorated. In addition, the alkali metal carbonate and / or cement granules may be 10 to 40%.
The pH of the entire composition can be adjusted within the range of weight%, and the pH is determined in consideration of the involvement of the pH with these components. The range of the target pH value is 5 to 9.

In the present invention, the presence of group essential additive selection substances is required in the composition, and these substances provide a nucleus for promoting the formation of flocs and also have an effect of adsorbing COD components, which are dissolved components in wastewater. Or it is deeply involved in improving the dewatering properties of the formed flocs. Therefore, a total of 10
To 40% by weight. In particular, the content of the bentonite soil mineral powder is 10 to 30% by weight.
It is preferable to set the weight% to enhance the effect of adsorbing and coagulating the COD component in the wastewater. Basically, it can be added within a range that does not impair the aggregation action.

Preferred examples of the soluble aluminum compound as one of the main components of the present invention include aluminum sulfate, aluminum chloride, polyaluminum chloride and the like. Further, as the iron salt compound of the present invention, ferrous chloride, ferrous sulfate, ferric sulfate, ferric polysulfate and the like are preferable.

The alkali metal carbonate or cement powder of the present invention includes sodium carbonate and sodium bicarbonate.
Particularly preferred are potassium carbonate, Portland cement and the like. The essential additive specified in the present invention is a compound or substance comprising a group of bentonite soil mineral powder and zeolite powder.

The bentonite soil mineral powder is mainly composed of silicic acid and alumina, which contains trace amounts of calcium oxide, potassium oxide, magnesium oxide, etc., and which is slightly alkaline in water. It is a granule to be produced, and the particle diameter of the constituent powder is preferably about 200 mesh pass to about 250 mesh on.

Further, the zeolite-based powder is mainly made by crushing natural soil minerals. The main constituents are alkali metals such as sodium and potassium, and the main constituents are alkaline earth metals such as calcium and magnesium. Is an aluminosilicate mineral containing water molecules in the form of water of crystallization. The granules employed in the present invention can be any natural or synthetic zeolite granules.

The field of application of the special solid fine powdery flocculant composition of the present invention is not particularly limited, and is not limited to civil engineering and construction site wastewater treatment and treatment water recycling, but also to ship bilge wastewater, ballast wastewater, It can be used as a coagulating sedimentation agent as a pretreatment for industrial wastewater treatment such as general oil-containing wastewater, steel rolling wastewater, water-soluble cutting oil wastewater, and other biological treatment processes. In addition, it is extremely useful in a wide range of fields, such as primary treatment of concentrated wastewater and addition as a flocculant at the time of dewatering of excess sludge and digested sludge drawn out of biological treatment, and thus greatly contributes to the protection of the global environment. is there.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples.

【Example】

Example 1 35% by weight of aluminum sulfate powder having an average particle diameter of about 150 μm, 25% by weight of soda ash powder having an average particle diameter of about 300 μm, and a cation having a particle diameter adjusted to about 150 mesh pass or less 10% by weight of polymer-based flocculant, about 7
A 100 g crude mixture of a bentonite powder having an average particle size of 5 μm at a weight ratio of 30% by weight was prepared.
The mixture was uniformly pulverized and mixed with a pulverization mixer of about 3000 revolutions per minute to obtain a mixed powder having an average particle size of about 60 μm. Using the obtained composition of the present invention as a raw water, an SS content of about 1200 mg /
l, pH 6.9, milky glass polishing wastewater was added at various ratios, and a flocculation test was conducted using a jar tester (150 rpm) to confirm the floc generation state.
To 5. The evaluation was carried out based on the stirring reaction time (sec) from the addition of the flocculant to the generation of the stable floc, the diameter (mm) of the floc formed by visual observation, the Toyo Filter Paper No. The clarity (kaolin turbidity), pH value, and the like of the filtrate using 5A filter paper were measured. The results were as shown in Table 1 below.

[0029]

[Table 1]

From the results in Table 1 above, the reaction time by stirring, the diameter of formed flocs by visual observation, the clarity of the filtrate, the pH value, and the like are all satisfactory in each of Experimental Examples 1 to 5. It turns out that the composition of the present invention is extremely innovative.

For comparison, in Comparative Experimental Example 1, as a similar composition outside the scope of the present invention, a similar composition was prepared except that bentonite was excluded from the components of Example 1 and calcium carbonate was used instead. It was used. In Comparative Example 2, about 10% PAC solution for industrial use and a cationic polymer flocculant (0.1% solution) were used in combination, and the pH was adjusted with a sodium hydroxide solution diluted with distilled water. Further, Comparative Experimental Example 3
The experiment was performed in the same manner as in Comparative Experimental Example 2 except that the target raw water was diluted three times with tap water. Under these conditions, a test using a jar tester was performed on the same polishing waste water as used in Example 1 until flocs were generated, and the evaluation results are shown in Table 2 below.

[0032]

[Table 2]

From the results in Table 2 above, it was found that the flocculation composition similar to the present invention did not provide a sufficient effect, and that the conventional method did not produce floc even if the raw water was treated as it was, By diluting it three times with tap water and adjusting the pH, generation of flocs was observed. However, comparing these results, it can be seen that they are extremely disadvantageous compared to the method of the present invention. Example 2 30% by weight of aluminum sulfate powder having an average particle diameter of about 150 μm, 20% by weight of soda ash powder having an average particle diameter of about 300 μm, and particle diameter of the powder below about 150 mesh pass The cationic polymer flocculant adjusted to 10 wt% and bentonite powder having an average particle diameter of about 75 μm were blended at a ratio of 40 wt%, and the average particle diameter was about 60 μm in the same manner as in Example 1. Was obtained. The obtained composition was added to raw water at various ratios as shown in Experimental Examples 6 to 10, and a flocculation test was conducted using a jar tester (150 rpm) to confirm the floc generation state in Example 1.
Was performed in the same manner as described above. About 1800 for SS as raw water
mg / l, pH 6.1, oil-containing wastewater of a blackish-brown automobile repair shop was used. Evaluation was performed in the same manner as in Example 1,
The results were as shown in Table 3 below.

[0034]

[Table 3]

From the results in Table 3 above, the reaction time by stirring, the diameter of the floc formed by visual observation, the clarity of the filtrate, the pH value, and the like are shown in Experimental Examples 6 to 10, respectively.
The results of the examples of the present invention are all satisfactory, and it can be seen that the composition of the present invention is extremely excellent.

For comparison, in Comparative Experimental Example 4, as a similar composition outside the scope of the present invention, the bentonite component was excluded from the components of Example 2, and calcium carbonate and zeolite components were each replaced by 20% by weight. The coagulant composition prepared in the same manner as in Example 1 was used in the same manner as in Example 1. In Comparative Example 5, pH was adjusted with a caustic soda solution diluted with distilled water using a combination of an industrial approximately 10% PAC solution and a strong cationic polymer flocculant (0.1% solution). Further, in Comparative Experimental Example 6, about 8% liquid sulfuric acid band solution for industrial use and a cationic polymer flocculant (0.1% solution) were used in combination, and palladium was diluted with caustic soda solution diluted with distilled water.
H adjustment was performed. Under these coagulation conditions, the same oil-containing wastewater as used in Example 2 was used in Example 2
A test was performed by a jar tester until flocking occurred in the same manner as described above, and the evaluation results are shown in Table 4 below.

[0037]

[Table 4]

From the results shown in Table 4 above, the same aggregating composition as that of the present invention cannot provide the same treatment effect as that of the examples of the present invention, and in the conventional method, the raw water is treated until the occurrence of floc is recognized. Required considerable time and trouble such as pH adjustment. Therefore, comparing these results with the method of the present invention, it can be seen that the agglomerated composition of the present invention is extremely excellent in agglutination reaction effect, and that the conventional method is disadvantageous in processing time and complexity.

Example 3 As raw materials, 30% by weight of aluminum sulfate powder having an average particle diameter of about 150 μm, 15% by weight of soda ash powder having an average particle diameter of about 300 μm, and 5% by weight of Portland cement were used. A mixture, 15 wt% of a cationic polymer flocculant whose particle diameter is adjusted to about 150 mesh pass or less, and a total of 100 g of bentonite powder having an average particle diameter of about 75 μm at a ratio of 35 wt%. The coagulant composition of the present invention was prepared by weighing and mixing uniformly by the same method as in Example 1.

The obtained composition of the present invention was added to raw water at various ratios as shown in Experimental Examples 11 to 15, and a flocculation test was conducted using a jar tester (150 rpm) to confirm the state of floc generation. A coagulation test was performed in the same manner as in the above. As raw water, SS content about 1500mg /
1, mud drainage from a tunnel construction excavation site with a pH of 6.7 was used. The evaluation was performed for the items shown in Table 5 below, and the experimental results were as shown in Table 5 below.

[0041]

[Table 5]

From the results shown in Table 5, the reaction time by stirring, the diameter of the formed floc by visual observation, the clarity of the filtrate, the pH value, and the like were all satisfactory in each of Experimental Examples 11 to 15. This shows that the composition of the present invention has an excellent aggregation effect.

For comparison, the wastewater from the excavation site of the tunnel construction used in Example 3 was used, and in Comparative Example 7, the composition of Example 3 was changed as a similar composition outside the scope of the present invention. A composition prepared in the same manner as in Example 1, except that the sulfuric acid band powder was 15% by weight, the soda ash powder was 10% by weight, the cationic polymer flocculant was 25% by weight, the calcium carbonate was 30% by weight, and the bentonite was 20% by weight. The thing was used.
As a conventional method, about 10% of industrial use
The test was performed using a PAC solution, a cationic polymer flocculant (0.1% solution), and a sodium hydroxide solution diluted with distilled water. Further, Comparative Example 9 was carried out using an industrial approximately 8% liquid sulfuric acid band solution, a cationic polymer flocculant (0.1% solution), and a caustic soda solution diluted with distilled water. The experimental results are as shown in Table 6 below.

[0044]

[Table 6]

From the results shown in Table 6 above, no effective effect was obtained with the flocculated composition similar to the present invention, and the conventional method required a considerable time and pH adjustment to treat raw water and generate flocs. Such troubles were necessary. Therefore, when these results are compared with the method of the present invention, the agglutinating composition of the present invention is extremely excellent in the agglutination reaction effect, and is extremely advantageous in shortening the processing time and avoiding complexity, which are difficult to compare with the conventional method. It is clear that

Example 4 30% by weight of ferric sulfate, 25% by weight of soda ash powder having an average particle diameter of about 300 μm, and a cationic polymer in which the particle diameter of the powder was adjusted to about 150 mesh or less. Coagulant 1
5% by weight of bentonite powder having an average particle diameter of about 75 μm was blended at a ratio of 30% by weight, and uniformly mixed in the same manner as in Example 1 to obtain a composition of the present invention. The obtained composition of the present invention was used at various ratios as shown in Experimental Examples 16 to 20, at an SS content of about 1100 mg / l and a pH of 6.
7. Oil concentration (n-hexane extracted substance) about 230 mg /
l of steel rolling wastewater, add a jar tester (150r
pm) was performed in the same manner as in Example 1 to confirm the flocculation state. For oil concentration,
For each of Experimental Examples 16 to 20, the measured value was 19,
The removal rates ranged from about 93 to 86% at 27, 29, 31, and 33 mg / l. Other evaluation results are as shown in Table 7 below.

[0047]

[Table 7]

From the results shown in Table 7, the reaction time by stirring, the diameter of the formed floc by visual observation, the clarity of the filtrate, the pH value, and the like were all satisfactory in Experimental Examples 16 to 20, respectively. . Even though the oily component concentration does not reach 5 mg / l or less on the basis of the release, it shows that the composition of the present invention is extremely excellent in effect as a flocculant. For comparison, the same steel rolling wastewater as used in Example 4 was used, and about 10% of a coagulant conventionally used in each of Comparative Examples 10 to 12 were used.
An agglutination test was performed using an AC solution, an approximately 8% sulfuric acid band solution, an approximately 38% ferric chloride solution, and a caustic soda solution diluted with a cationic polymer coagulant (0.1% solution) and distilled water. The experimental results are as shown in Table 8 below.

[0049]

[Table 8]

From the results shown in Table 8 above, in the conventional method, it takes a considerable time and pH to treat raw water and generate flocs.
Adjustment was required, but the results were still inadequate. Therefore, when these results are compared with the method of the present invention, the flocculation composition of the present invention is extremely excellent in flocculation reactivity through this comparative experiment, and the processing time and the complexity are difficult to compare with the conventional method. Obviously, it is also very advantageous in avoidance.

[0051]

The special powder coagulant of the present invention is a composite composition comprising an inorganic coagulant and an auxiliary, an organic polymer coagulant, and other functional essential additives uniformly mixed. , The coagulation reactivity in the wastewater to be treated is uniform, exhibiting an extremely excellent industrial effect in terms of reaction time and work simplicity compared to the conventional method using coagulants I can do it. In particular, in the present invention, the reactivity with an organic polymer flocculant having a moderate reactivity compared to other inorganic components which act synergistically in the composition of the composition can be improved by using the organic polymer flocculant which has not been conventionally carried out. By blending the agent into the powder as a finer powder than usual, complete treatment by adding a single product to the wastewater to be treated of only the special solid fine powdery flocculant composition of the present invention was achieved, By this method, the coagulation and sedimentation treatment of various wastewaters can be very simply adopted only by a simple addition and stirring step, and greatly contributes industrially in various wastewater treatment fields.

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[Procedure amendment]

[Submission date] October 31, 1996

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Name of invention

[Correction method] Change

[Correction contents]

Patent application title: Special solid fine powdery flocculant composition and water treatment
Method

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] Claim 4

[Correction method] Change

[Correction contents]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction contents]

The particle size of the fine powder of the polymer flocculant targeted in the present invention is smaller than 80 mesh pass , preferably 1
It is extremely important for the composition of the present invention that the fine powder is smaller, such as a 00 mesh pass. In the case of wastewater treatment, coarser particles do not exhibit a uniform dissolution rate characteristic as the coagulant of the present invention, which adversely affects the promptness of the coagulation reaction surface and increases the partial tackiness of the floc. In some cases, the object of the present invention is difficult to achieve.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction contents]

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples.

EXAMPLES Example 1 35% by weight of aluminum sulfate particles having an average particle size of about 150 μm, 25% by weight of soda ash particles having an average particle size of about 300 μm, smaller than about 150 mesh pass
Dia flock Co. cationic polymer flocculant which had been adjusted to a particle size had KP1200B 10 wt%, to create a 100g crude mixture of bentonite powder granules having an average particle size of about 75μm with 30 wt% metering rate, which About 30 minutes per minute
The mixture was uniformly pulverized and mixed with a pulverization mixer having a rotation of 00 to obtain a mixed powder having an average particle size of about 60 μm. The obtained composition of the present invention was used as raw water in an SS content of about 1200 mg / l and a pH of 6.
No. 9 was added to the milky white glass polishing wastewater at various ratios, and a flocculation test was conducted as Jar Testers (150 rpm) to confirm flocculation conditions as Experimental Examples 1 to 5. The evaluation was carried out based on the stirring reaction time (sec) from the addition of the flocculant to the generation of the stable floc, the diameter (mm) of the floc formed by visual observation, the Toyo Filter Paper No. The clarity (kaolin turbidity), pH value, and the like of the filtrate using 5A filter paper were measured. The results were as shown in Table 1 below.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction contents]

For comparison, in Comparative Experimental Example 1, a similar composition outside the scope of the present invention was prepared in the same manner as in Example 1, except that bentonite was excluded and calcium sulfate was used instead. And the experiment method of Example 1
Performed according to the law . In Comparative Example 2, about 1
0% PAC solution and cationic polymer flocculant KP1200
B (0.1% solution) was used in combination, and the pH was adjusted with a sodium hydroxide solution diluted with distilled water. Furthermore, in Comparative Experimental Example 3, an experiment was performed in the same manner as in Comparative Experimental Example 2, except that the target raw water was diluted three times with tap water. Under these conditions, Example 1
A test using a jar tester was carried out on the same polishing wastewater as used in Example 1 until flocs occurred, and the evaluation results are shown in Table 2 below.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction contents]

From the results in Table 2 above, it was found that the flocculation composition similar to the present invention did not provide a sufficient effect and that the conventional method did not produce floc even if the raw water was treated as it was, By diluting with water three times and adjusting the pH, generation of flocs was observed. But,
By comparing these results, it can be seen that the method is extremely disadvantageous compared to the method of the present invention. Example 2 30% by weight of aluminum sulfate particles having an average particle size of about 150 μm, 20% by weight of soda ash particles having an average particle size of about 300 μm, smaller than about 150 mesh pass
There granular material Kachio <br/> down polymer flocculant KP1200B 10 wt% particle size diamond flocs Co. adjusted to the approximately 75μ
40% by weight of bentonite powder having an average particle size of m
And a powder composition having an average particle size of about 60 μm was obtained in the same manner as in Example 1. The obtained compositions were added to raw water at various ratios as shown in Experimental Examples 6 to 10, and a flocculation test was conducted in the same manner as in Example 1 by using a jar tester (150 rpm) to confirm the state of floc generation. . As raw water, SS content is about 1800mg / l, pH
The oil-bearing wastewater of 6.1 was used as a black-brown automobile repair shop.
The evaluation was performed in the same manner as in Example 1, and the results were as shown in Table 3 below.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction contents]

For comparison, in Comparative Experimental Example 4, as a similar composition outside the scope of the present invention, the bentonite component was excluded from the components of Example 2, and calcium sulfate and zeolite components were each replaced by 20% by weight. The aggregating agent composition was prepared in the same manner as in Example 1 by using a mixture prepared in the same manner as in Example 1, and was carried out in accordance with the experimental method of Example 1 . Further, Comparative Experiment Example 5 as a conventional method, about 10% PAC solution and Dialog industrial
Strong cationic polymer flocculant KP12 manufactured by Earflock
00B (0.1% solution) was used in combination, and the pH was adjusted with a sodium hydroxide solution diluted with distilled water. Furthermore, as a conventional method in Comparative Example 6, about 8% liquid sulfuric Al industrial
Miniumu solution and cationic polymer flocculant KP1200B
(0.1% solution), and the pH was adjusted with a sodium hydroxide solution diluted with distilled water. Under these coagulation conditions, a test using a jar tester was performed on the same oil-containing wastewater as used in Example 2 until floc was generated in the same manner as in Example 2, and the evaluation results were shown in Table 4 below. Shown in

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction contents]

Example 3 As raw materials, 30% by weight of aluminum sulfate powder having an average particle diameter of about 150 μm, 15% by weight of soda ash powder having an average particle diameter of about 300 μm, and 5% by weight of Portland cement were used. Mixture, less than about 150 mesh pass
Cationic polymer flocculant K adjusted to the particle size of Sai granular material
P1200B 15% by weight of bentonite powder having an average particle size of about 75 μm was weighed and blended in a total amount of 35% by weight in a total amount of 100 g, and uniformly mixed by the same method as in Example 1 to obtain a flocculant of the present invention. A composition was made.

[Procedure amendment 10]

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[Correction target item name] 0043

[Correction method] Change

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For comparison, the tunnel used in Example 3 below was used.
In comparative experiment 7 using drainage mud drainage from
As a similar composition outside the scope of the invention, the composition of Example 3
Change and sulfuric acidaluminum15% by weight powder, soda ash powder
Granules 10% by weight, cationic polymer flocculantKP1200
B25% by weight,Sulfuric acid30% calcium by weight, bentoni
20% by weight in the same manner as in Example 1.
Using an adultPerformed according to the experimental method of Example 1.Was.
As a conventional method, about 10% of industrial use
PAC solution, cationic polymer flocculantKP1200B
(0.1% solution), caustic soda solution diluted with distilled water
It was carried out using. FurtherAs a conventional methodIn Comparative Example 9
Is about 8% liquid sulfuric acid for industrial usealuminumSolutions and cations
Polymer flocculantKP1200B(0.1% solution), distillation
The test was performed using a sodium hydroxide solution diluted with water. That
The experimental results are as shown in Table 6 below.

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Example 4 Ferric sulfate 30% by weight, soda ash powder having an average particle size of about 300 pm 25% by weight, about 150 mesh pass .
15% by weight of a cationic polymer flocculant KP1200B adjusted to the particle size of a very small powder and 15% by weight of bentonite powder having an average particle diameter of about 75 μm were blended at a ratio of 30% by weight, as in Example 1. The composition of the present invention was uniformly mixed by the method described above. The obtained composition of the present invention was subjected to an SS content of about 1100 at various ratios as shown in Experimental Examples 16 to 20.
mg / l, pH 6.7, oil concentration (n-hexane extracted substance) was added to steel rolling wastewater of about 230 mg / l, and a flocculation test similar to that of Example 1 was performed using a jar tester (150 rpm) to confirm the state of floc generation. Made by the way. Regarding the oil concentration, the measured values were 19, 27, 29, 31, and 33 mg / l for each of Experimental Examples 16 to 20.
At a removal rate of about 93 to 86%. Other evaluation results are as shown in Table 7 below.

[Procedure amendment 12]

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[Correction target item name] 0048

[Correction method] Change

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From the results in Table 7 above, it was found that the reaction was
And the clarity of the filtrate of the diameter of the generated floc by visual observation
And pH values, etc., in each of Experimental Examples 16 to 20
I was in a satisfactory state. Release only oil concentration
Effective as a flocculant even if it does not fall below the standard 5 mg / l
Shows that the composition of the present invention is extremely excellent
ing. For comparison, the same steel used in Example 4 below
Using the rolling drainage, three points of Comparative Experimental Examples 10 to 12
And about 10% of a coagulant conventionally used, respectively.
C solution, about 8% sulfuric acidaluminumSolution, about 38% chloride
Ferrous solution and cationic polymer flocculantKP1200B
(0.1% solution) and caustic soda solution diluted with distilled water
Was used to perform an aggregation test. Table 8 shows the experimental results.
As shown. ────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 6, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

The special solid fine powdery flocculant composition of the present invention can be obtained by simultaneously blending the specific compounds constituting the present invention in powder form and mixing them uniformly. As the blending ratio of the composition, it is necessary to variably correspond to each other, but the basic composition is determined by the blending amount of the soluble aluminum or soluble iron salt compound as the flocculant component and the natural or synthetic polymer flocculant. You. An alkali metal carbonate and / or cement powder as a pH adjuster ,
Calcium compound, dioxide as a mixing aid of the basic composition
Inert substances such as titanium, sodium sulfate, and diatomaceous earth, and as the third component, one selected from bentonite soil mineral powder or zeolite powder as an essential additive selection substance.

Claims (10)

[Claims] 1. A flocculant comprising a soluble aluminum compound or a soluble iron salt compound, a natural or synthetic polymer flocculant, and an alkali metal such that an aqueous solution of the flocculant exhibits a pH value near neutrality. Blended carbonate and / or cement powder, and further bentonite soil mineral powder,
Alternatively, a special solid fine powder coagulant composition characterized by blending one selected from zeolite-based powders. 2. The method according to claim 2, wherein the soluble aluminum compound is
The special solid fine powder coagulant composition according to claim 1, wherein any one of aluminum sulfate, aluminum chloride and polyaluminum chloride is used. 3. The special solid fine powder according to claim 1, wherein any one of ferrous chloride, ferrous sulfate, ferric sulfate, and ferric polysulfate is used as the soluble iron salt compound. Coagulant composition. 4. The special solid fine powder coagulant composition according to claim 1, wherein a fine powder natural or synthetic polymer coagulant of 100 mesh or more is used as said synthetic polymer coagulant. 5. The special solid fine powder flocculant composition according to claim 1, wherein a cationic natural or synthetic polymer flocculant is used as said synthetic polymer flocculant. 6. The natural polymer flocculant as β-1,3
The special solid fine powder coagulant composition according to any one of claims 1 to 5, wherein a coagulant obtained from an acidic polysaccharide polymer mainly containing glucan is used. 7. The special solid fine powder coagulant composition according to claim 1, wherein sodium carbonate, sodium bicarbonate, potassium carbonate or Portland cement is used as said alkali metal carbonate and / or cement powder. Stuff. 8. The composition of the present invention, wherein the weight percentage of the composition is 100%, the soluble aluminum compound or the soluble iron salt compound is 15 to 50% by weight, and the natural or synthetic polymer coagulant is 0.5 to 25% by weight. %, 10 to 40% by weight of alkali metal carbonate and / or cement powder,
The special solid fine powdery flocculant composition according to any one of claims 1 to 7, wherein 10 to 40% by weight of one selected from a bentonite soil mineral powder or a zeolite powder is uniformly mixed to form a composition. . 9. The method according to claim 1, wherein the bentonite soil mineral powder is 10
The special solid fine powder type flocculant composition according to claim 1, wherein the composition comprises 1 to 30% by weight. 10. A wastewater treatment method comprising adding the special solid fine powdery flocculant composition according to any one of the above-mentioned claims to wastewater to be treated and causing a flocculation reaction with stirring. .