JPH1057712A - Powdery flocculant composition and water processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a powdery flocculant compsn. which can cause a flocculation reaction of contaminants floating and present in a waste water in a short time only by adding and stirring or dispersing the flocculant into the waste water to be processed, and to provide a water processing method using this compsn. SOLUTION: This compsn. is composed of an inorg. powder material, natural or synthetic polymer flocculant, and if necessary, other functionally necessary additives. The inorg. powder essentially consists of active silicon dioxide and alumina and shows at least 15mV absolute max. zeta potential. The polymer flocculant is soluble in water and is in a fine powder state compared to the state usually used. These materials are uniformly mixed into a powder state to obtain the functional powder flocculant compsn. This flocculant compsn. in a single state is directly added and stirred in the water to be processed, and the flucculation reaction is completed in a wide pH range. The produced floc excellent in dimensional stability and a dehydrating property is separated and discharged from the system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a powdery flocculant composition and a water treatment method using the same. More specifically, the present invention relates to a composition of the present invention formed by blending a specific substance, and a technique of applying the composition to water to be treated to aggregate pollutants in a short time and to form a floc which can be easily separated.

[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 most cases, the coagulant is handled as an aqueous solution for on-site work, so that the addition amount can be controlled relatively accurately even with a small amount.

[0003] On the other hand, however, the cost of storing and transporting the flocculant is high. In particular, the polymeric flocculant often dissolves completely on site, requiring a lot of time and labor for preparation, and also limits the effective action retention time. Suffering from various problems. Therefore, if a method that not only requires a considerable amount of time for the treatment as a whole but also ensures the reaction and residence time satisfactorily is adopted, a high initial cost is required as a facility opening cost, which is a favorable situation. Absent.

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 a treatment condition suitable for this have been studied. In addition, modification of the flocculant itself is also being studied. For example, as a means of increasing the agglomeration treatment speed or improving the dehydration of the formed floc, in addition to the conventional aggregating agent, diatomaceous earth, clay, gypsum, limes, calcium carbonate, etc. are added as auxiliary agents. PH intended to improve process or wastewater treatment process
Various improvement measures have been studied and reported, such as development of a coagulant composition having a regulating function.

As one example, Japanese Patent Application Laid-Open No. 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.

[0006] As the wastewater to be subjected to these coagulation treatments,
Not only general factory drainage, but also muddy water from subway construction sites, shielding drainage in tunnel construction, concrete drainage from ready-mixed concrete sites, etc. In many cases, simple and easy equipment is used to cope with the situation, and there is a demand for a more reliable method that can be simply processed in practical use.

[0007]

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. .

[0008] In addition, with respect to the remedies that have been proposed by using various types of coagulant compositions, when applied to a wide range of wastewater, a favorable floc is not always generated.
Further, a preferable supernatant water is not always obtained after separation of the formed flocs. As described above, many problems remain in the practical field, and it is still necessary to fundamentally study the development in terms of the mixed composition or the types and distribution of the components.

[0009]

Means for Solving the Problems In view of such circumstances, the present inventors have set out to solve the above-mentioned problems with ease of handling and low initial cost. Aggregates pollutants in wastewater in a short time,
We have made intensive studies to develop a powdery flocculant composition that is a stable floc with good dehydration properties. As a result, a powdery flocculant composition which exerts a flocculating action on a relatively wide range of wastewater in a very short time, and the formed floc is stable, compact and has good dewatering properties, and wastewater treatment using this composition Invented a method.

[0010] That is, the gist of the present invention is to provide inorganic powders containing active silicon dioxide and alumina as main components and exhibiting a maximum zeta potential of at least 15 mV in absolute value, and water-soluble natural or synthetic particles. And a waste water treatment method using the composition.

[0011]

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 a specific special composition to be formed, and the composition of the present invention has an aggregating action based on the synergistic action of each component, and is easy with a conventionally known aggregating agent. It exerts an extremely powerful action and effect that could not be realized.

The first feature of the composition of the present invention is that the effect can be obtained only by adding a single powder coagulant composition to the treated wastewater, so that conventionally used inorganic coagulants, inorganic salts and The effect obtained by introducing a polymer flocculant or the like into wastewater with complicated steps can be easily achieved. That is, the point is that the aggregation effect can be exhibited without impairing the properties of both the aggregation effect and the crosslinking effect. For this reason, it is particularly important that the polymer flocculant is incorporated as finely powdered as possible. As a result, the action time of the individual polymer flocculant fine particles almost coincides with the coexisting inorganic flocculant and other inorganic fine particles blended as other additives, and each component is added to the wastewater without being isolated. The agglutination reaction is completed in a very short time because the agglutination reaction is dissolved or dispersed.

The second feature of the composition of the present invention is that the range of the agglutination reaction is extremely wide, for example, floc can be formed in a wide range such as 3 to 11 at the pH value of the target waste water, and a special p
The point is that it can be applied without requiring H adjustment. Although the reason for this is not clear, the absolute value of the zeta potential in water of the main component of the flocculant composition of the present invention is related to the fact that the potential is maintained at an extremely high level in a considerable pH range. Estimated. Therefore, floc can be substantially generated even if labor for pH adjustment equipment by injecting a chemical such as an acid or an alkali which is usually required in the coagulation treatment step is saved.

The third feature of the composition of the present invention is that the formed floc itself has an adsorbing effect, and the dissolved component CO
It is also useful for the adsorption removal of D, but by further blending at least one selected from bentonite soil mineral powder or zeolite powder, the above-mentioned main component of the present invention becomes the core of the generated floc, Adsorption and coagulation can be expected as synergistic effects with the respective components.
Furthermore, while helping to remove COD, which is a dissolved component in water, the obtained floc is also stably strong and has improved dewatering properties. In particular, an excellent effect is observed in combination with the bentonite soil mineral powder. This effect
Even when this floc is separated as a cake and dewatered, it is advantageous in terms of dewatering equipment, and a dewatered cake having a low water content is obtained, and as a result, it is extremely useful for protecting the global environment.

The fourth feature of the composition of the present invention is that, as described above, since wastewater treatment can be carried out simply and reliably, wastewater generated in civil engineering and construction sites, etc., which was extremely difficult to treat directly at conventional sites, can be obtained. Not only is it possible to easily process and recycle the waste, but also at sites where conventional direct treatment is performed, more compact equipment and more reliable treatment is possible, and the amount of waste finally generated is lower than before. Is much less.

In the present invention, it is extremely important to constitute a composition containing, as an essential component, a granular material mainly composed of active silicon dioxide and alumina having a high level of zeta potential as an absolute value. By combining with a polymer flocculant, the excellent effects of the present invention can be exhibited. Here, the method for obtaining the powdery granules containing the active silicon dioxide and alumina as the main components specified in the present invention is not particularly limited.

For example, a composition obtained by activating a fine particle surface by mixing and grinding a coarse particle mixture obtained by mixing a coarse particle mainly containing silicon dioxide and an alumina coarse particle under a high shear force. A method of obtaining, a method of applying a chemical treatment to the surface of the once-pulverized and mixed granules, or a method of activating the surface of the pulverized and mixed granules by heat treatment, or an electric high-energy irradiation treatment or the like. The pulverized mixture particles are activated by a method of surface activation or the like to increase the absolute value of zeta potential in water.

The mixing ratio of silicon dioxide and alumina is set to a range in which the zeta potential is high in order to increase the absolute value of the zeta potential in water and to maintain a stable neutralizing ability of the colloid particles in water in a wide pH range. In the setting of the flocculant function, which is a minus advantage in some regions, and a plus advantage in a certain region, the present inventors have determined that at least 50% by weight of silicon dioxide and at least 5% by weight of alumina are required for a wide range of unspecified wastewater. On the other hand, it has been experimentally confirmed that it is particularly preferable. Outside of these ranges, the wastewater containing inorganic substances intended in the present invention has a drawback that a prompt coagulation effect is hardly exhibited.

The coarse particles containing silicon dioxide used in the present invention are commercially available quartz rocks or silica sands. The coarse particles which preferably account for about 99% of the pure silicon dioxide are selected, and this is used for ball mills and the like. Mainly at least 250 in the crusher
It can be easily obtained by pulverizing to a mesh under level. These usually have a zeta potential of about minus 40 mV measured in distilled water having a pH value of about 4 to 7. Further, as described in detail below, natural silica or the like containing silicon dioxide and alumina as the main components at the same time is selected, and pulverized in the same manner as described above using an activatable object from among these, the present invention A mixed powder containing both required essential components can be obtained at once.

The alumina used in the present invention may be, for example, a commercially available, spherical, industrial activated alumina having a diameter of about 1.4 to 8 mm, which is pulverized by a pulverizing mill. And its zeta potential is usually about plus 30 mV, p at pH 4-5.
An H value of 9 to 10 indicates about minus 45 mV.

On the other hand, from the naturally occurring quartzite, quartzite or siliceous schist-based minerals and similar ore fragments, a component ore containing silicon dioxide and alumina as the main components required in the present invention is selected or blended. Is activated by grinding with a ball mill or the like under a high shearing force, or the activated silicon dioxide and alumina used in the present invention are used as main components even if the surface of the pulverized particles is further subjected to an activation treatment such as a chemical treatment or a heat treatment. Can be obtained. This can be achieved by selecting and adopting powders obtained from these natural products that exhibit a high level of the absolute value of the zeta potential which is the subject of the present invention. The measurement of the zeta potential is generally performed using laser Doppler electrophoresis.

The fine powdery polymer flocculant used in the present invention may be either natural or synthetic, and in particular, nonionic and cationic polymer flocculants are preferable for synthetic ones. These synthetic polymer flocculants used in the present invention can be any commercial products. On the other hand, in the natural system, various polysaccharides can be used,
In particular, 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 preferable.

In order to obtain the powdery flocculant composition of the present invention,
It is important to homogenously pulverize and mix mainly the above-mentioned powdered granules mainly composed of activated silicon dioxide and alumina and a powdery polymer flocculant. At this time, it is preferable in terms of the composition of the present invention that the particle size distribution of each component is mainly a fine powder of 80 mesh under. In particular, it is extremely important for the composition of the present invention that the fine powder of the polymer flocculant is finer, such as under 80 mesh, preferably under 100 mesh. Coarse particles may not show uniform dissolution rate characteristics on the flocculant effect surface of the present invention in the treatment of wastewater, and thus adversely affect the promptness on the flocculation reaction surface,
There is a concern that the partial tackiness of the flock will unnecessarily increase.

In the present invention, a powdery flocculant composition having a specific composition can be easily obtained by simultaneously mixing the specific compounds constituting the present invention in powder form and mixing them uniformly. As the composition ratio of the composition, all of them need to correspond variably, but as a basic composition, the main component is activated silicon dioxide and alumina which are coagulant components, and the absolute value of the maximum value of the zeta potential is at least 15 mV. Preferably, it is determined by the blending amount of the powder and granules showing 20 mV and the natural or synthetic polymer flocculant. To this, an alkali metal carbonate and / or cement powder as a pH adjuster and one selected from bentonite soil mineral powder or zeolite powder as a third component are blended as an additive selection substance. You can do it.

If each material is blended in the powder coagulant representative of the present invention, the composition weight ratio of the whole composition is 1
0%, 70 to 99.5% by weight of a granular material mainly composed of active silicon dioxide and alumina specified in the present invention, and 0.5% of a water-soluble natural or synthetic polymer flocculant.
To 30% by weight to obtain a composition. In the composition ratio of the composition shown here, the content of the polymer flocculant must be at least 0.5% by weight. If the content is less than this, the effect is slow or the reaction time is extremely long. On the other hand, if the amount is more than 30% by weight, the dewatering property of the formed floc after the reaction is extremely deteriorated, and the ratio of the amount of the basic constituent powder that maintains the zeta potential, which is important in the present invention, is reduced. Not preferred. The compounding ratio of the powder is preferably at least about 70% by weight.

When at least one kind selected from the above bentonite soil mineral powder or zeolite powder is further added to these compositions, the composition weight ratio of the whole composition is set to 100%. 70 to 94.5% by weight of a granular material mainly composed of active silicon dioxide and alumina specified in the present invention, 0.5 to 30% by weight of a water-soluble natural or synthetic polymer flocculant, and bentonite At least one member selected from the group consisting of soil mineral powder or zeolite powder is uniformly mixed at 5 to 30% by weight to obtain a composition. In the composition ratio of the composition shown here,
When enhancing the dewatering property of formed floc and the adsorbability of COD components in treated water to the composition as the basis of the present invention, in addition to the required polymer flocculant, bentonite soil mineral powder or granules as a third component or A zeolite-based powder is blended. At this time, it is necessary to add at least 5% by weight alone or as a mixture. However, if the content is more than 30% by weight, it is not preferable because the coagulation effect based on the present invention is extremely reduced.

As the alkali metal carbonate or cement powder used as the pH adjuster in the present invention, sodium carbonate, sodium bicarbonate, potassium carbonate, Portland cement and the like are particularly preferable. The additive employed as the third component in the present invention is a compound or substance comprising a group of bentonite soil mineral powder and zeolite powder.

As the bentonite soil mineral powder,
The main component is silicic acid and alumina, which contains trace amounts of calcium oxide, potassium oxide, magnesium oxide, etc., and is a granule made from soil minerals that show slight alkalinity in water. Usually, a particle size of about 200 mesh pass to 250 mesh on is preferable.

The zeolite-based particles are 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 powdery flocculant composition of the present invention is not particularly limited, and is not limited to wastewater treatment and recycle of treated water at civil engineering construction sites, but also bilge wastewater, ballast wastewater, and general oil-containing wastewater. It can be used as a coagulating sedimentation treatment agent for pre-treatment of industrial wastewater treatment such as 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 Silica sand containing silicon dioxide at a high purity of about 99.8% was pulverized by a pulverizing mill so as to have a size of 350 mesh under (particle size of about 44 μm). 75% by weight, about 99.8% milled to 250 mesh under (particle size of about 60 μm) and about 20% by weight of high purity γ-form aluminum powder, and non-ionic (hereinafter A ) Or cationic (hereinafter abbreviated as B) synthetic polymer flocculants, each of which is selected from the group consisting of 5 types.
% By weight to prepare a crude mixture having a total amount of 100 g, which was further uniformly pulverized and mixed with a pulverization mixer of about 3000 rpm for 1 minute to obtain a composition of the present invention having an average particle size of about 44 μm. Was.

The obtained composition of the present invention was converted to S
An example of an agglutination test in which a S content was added to milky white glass polishing wastewater of about 1200 mg / l and pH 6.9 at various ratios as shown in Table 1 and a jar tester (150 rpm) was used to confirm the state of floc generation. Performed as 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.
Here, Experimental Examples 1 to 3 contain A flocculant and others
It is a flocculant.

In addition, the mixed powder of the silica powder having a high purity of about 99.8% containing silicon dioxide and the γ-form aluminum powder having the same high purity as that of the above-mentioned predetermined amount is mixed. Was measured by laser Doppler electrophoresis, and the average of four measurements was minus 29.
6 mV. As a specific measuring method, a small amount of a powder sample was poured into about 30 ml of distilled water, subjected to ultrasonic dispersion treatment for about 3 minutes, and then allowed to stand for 30 minutes.
After filtration through a filter of m. The pH value of the measurement solution was 6.8 to 6.9. The experimental results of the embodiment of the present invention described above are as shown in Table 1 below.

[0034]

[Table 1]

From the results in Table 1 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 all satisfactory in each of Experimental Examples 1 to 5. It turns out that the composition of the present invention is extremely innovative.

COMPARATIVE EXAMPLE 1 For comparison with the present invention, in Comparative Experimental Example 1, as a similar composition outside the scope of the present invention, a mixed powder of silicon dioxide and aluminum powder of the components of Example 1 was used. The same body was used as in Example 1, except that the zeta potential was −9.4 mV as an average of four measurements when a predetermined amount was mixed, as in Example 1. In Comparative Experimental Example 2, a commercially available industrial product, about 10% PAC solution and a nonionic polymer coagulant (0.1% solution) from Diafloc were used in combination, and a caustic soda solution diluted with distilled water was used. The pH was adjusted. 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 twice with tap water. Under these conditions, a test with 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.

[0037]

[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 twice with tap water and adjusting the pH, generation of some flocs was observed.
However, it turns out that these results are extremely disadvantageous when compared with the method of the present invention.

Example 2 A natural quartzite consisting of about 80% of silicon dioxide, about 10% of alumina component and about 10% of other components was subjected to 25 ball milling.
It was pulverized so as to have 0 mesh under (particle size of about 60 μm) to obtain a rattan powder. When the zeta potential of this powder was checked in the same manner as in Example 1, the average value was minus 29.6 mV. 90% by weight of the rock powder prepared here and 10% by weight of a strong cationic synthetic polymer flocculant from Diafloc as a commercially available flocculant were mixed at a ratio of 10% by weight to prepare a crude mixture having a total amount of 100 g. The mixture was further uniformly pulverized and mixed with a pulverization mixer of about 3000 rotations for 1 minute to obtain a composition of the present invention having a size of 350 mesh under (average particle size of about 44 μm).

The obtained composition of the present invention 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 state of floc generation. Was performed in the same manner as described above.
As the raw water, a black-brown oil-containing wastewater having a SS content of about 1800 mg / l and a pH of 6.1 was used. Evaluation,
The procedure was performed in the same manner as in Example 1, and the results were as shown in Table 3 below.

[0041]

[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 were determined 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.

Comparative Example 2 For comparison with the present invention, in Comparative Experimental Example 4, an experiment similar to that of Example 2 was performed using a similar composition outside the scope of the present invention. That is, a natural quartzite composed of about 80% of silicon dioxide, about 10% of an alumina component, and about 10% of other components is pulverized by a ball mill so as to have a 250 mesh under (particle size of about 60 μm). Powder was obtained. When the zeta potential of this powder was checked in the same manner as in Example 1, an average value of -10.2 mV was shown. 90% by weight of the obtained rock powder and 10% by weight of a strong cationic synthetic polymer flocculant from Diafloc as a commercially available flocculant were mixed at a ratio of 10% by weight to prepare a crude mixture having a total amount of 100 g. The mixture was further uniformly pulverized and mixed with a pulverization mixer of about 3000 revolutions for 1 minute to obtain a similar composition having a mesh size of 350 mesh (average particle size of about 44 μm) outside the range of the present invention.

On the other hand, in Comparative Experimental Example 5, an industrial commercial product was used.
About 10% PAC solution was used in combination with Diafloc's nonionic polymer flocculant (0.1% solution), and the pH was adjusted with a sodium hydroxide solution diluted with distilled water. Furthermore, in Comparative Experimental Example 6, an experiment was performed in the same manner as in Comparative Experimental Example 4, except that the target raw water was diluted three times with tap water. Under these conditions, at various ratios as shown in Table 4 below, added to raw water,
A flocculation test for confirming the state of floc generation by a jar tester (150 rpm) was performed in the same manner as in Example 1. As raw water, SS content is about 1800mg / l, pH6.
The oil-containing wastewater of blackish brown car maintenance shop No. 1 was used. The evaluation was performed in the same manner as in Example 1, and the results were as shown in Table 4 below.

[0045]

[Table 4]

From the results in Table 4 above, similar compositions outside the scope of the present invention do not provide the same degree of processing effect as in the examples of the present invention. Further, in the conventional method, considerable time and troubles such as pH adjustment were required to treat raw water to generate flocs, but the results were still insufficient. Therefore, when the results of these comparative examples are compared with the method of the present invention, the agglomerated composition of the present invention is extremely excellent in agglutinating reactivity, and the shortening of processing time and the avoidance of complexity, which are difficult to compare with the conventional method. It is clear that is very advantageous in

Example 3 Silica sand having a high purity of about 99.8% of silicon dioxide was crushed by a crushing mill so as to have a size of 350 mesh under (particle size of about 44 μm). The powder was 75% by weight, about 99.8% milled to 250 mesh under (particle size of about 60 μm) and 25% by weight of high-purity γ-aluminum powder, and further added for about 3 minutes for about 3 minutes.
The mixture was uniformly pulverized and mixed with a pulverization mixer having a rotation of 000 to obtain a mixed powder having an average particle size of about 44 μm. The zeta potential showed minus 28.8 mV.

70% by weight of this mixed powder, 5% by weight of one selected from nonionic (hereinafter abbreviated as A) or cationic (hereinafter abbreviated as B) synthetic polymer flocculants as a flocculant, and 5% by weight, further commercially available One of bentonite powder (hereinafter abbreviated as C) or zeolite powder (hereinafter abbreviated as D) is mixed and mixed at 25% by weight, and is uniformly pulverized and mixed with a pulverization mixer of about 3000 revolutions for 1 minute. 100 g of various powdery compositions of the present invention adjusted to a particle size of about 44 μm were obtained. All the polymer flocculants used were Diafloc products.

The obtained composition of the present invention was converted to S
An agglutination test was conducted by adding a variety of ratios to the milky white glass polishing wastewater having an S content of about 1200 mg / l and a pH of 6.9 as shown in Table 5 and using a jar tester (150 rpm) to check the state of floc generation. 11 to 14
It was carried out as. Here, a combination of A and C is shown in Experimental Example 11, a combination of A and D is shown in Experimental Example 12, a combination of B and C is shown in Experimental Example 13, and a combination of B and D is shown in Experimental Example 14. I have. Evaluation of these experimental examples was based on the stirring reaction time (sec) from the addition of the flocculant to the generation of stable flocs, the diameter of the formed flocs (mm) by visual observation, and Toyo Filter Paper No. 5
The clarity (kaolin turbidity) and pH of the filtrate by A filter paper
The evaluation was performed for values and the like. The experimental results of this example are shown in Table 5 below.
As shown in FIG.

[0050]

[Table 5]

From the results shown in Table 5, the reaction time by stirring, the diameter of formed floc by visual observation, the clarity of the filtrate, the pH value, and the like are all satisfactory in each of Experimental Examples 12 to 14. In particular, all of the examples were similarly made of Toyo Filter Paper No. It was confirmed that the filtration residue after filtration with the 5A filter paper adhered little to the filter paper, and was excellent in dehydration. Therefore, it is understood that the composition of the present invention is extremely innovative.

[0052]

The powdery flocculant composition of the present invention uses an inorganic powdery granule containing active silicon dioxide and alumina as main components and having a maximum zeta potential of at least 15 mV in absolute value. This is a composite composition composed of a natural or synthetic polymer coagulant and other functional essential additives as required, but the coagulation reactivity in the wastewater to be treated is uniform. However, as compared with the conventional method using a flocculant, an extremely excellent industrial effect can be exhibited in terms of reaction time and work simplicity.

In particular, in the present invention, the reactivity of the other components acting synergistically in the composition with an organic polymer flocculant having a moderate reactivity is reduced to a fine powder form which has not been conventionally carried out. By blending in the powder as a, in that the completion treatment by adding a single item to the wastewater to be treated of only the powdery coagulant composition of the present invention was achieved, and this method was performed only by a simple addition and stirring step. The effect of coagulation and sedimentation of various wastewaters can be adopted very simply.
It greatly contributes industrially in various wastewater treatment fields.

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[Procedure amendment]

[Submission date] October 28, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 7

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0023

[Correction method] Change

[Correction contents]

In order to obtain the powdery flocculant composition of the present invention,
It is important to homogenously pulverize and mix mainly the above-mentioned powdered granules mainly composed of activated silicon dioxide and alumina and a powdery polymer flocculant. In this case, it is preferable in terms of the composition of the present invention that the particle diameter distribution of each component is mainly a fine powder smaller than 80 mesh pass . Especially,
The particle size of the fine powder of the polymer flocculant is mainly 80 mesh
Path as preferably of 100 mesh pass, it is extremely important configuration compositions of the present invention is smaller <br/> fine powder. In the case of wastewater treatment with coarse particles, when there is no uniform dissolution rate characteristic in terms of the flocculant effect of the present invention, there is a bad effect on the promptness in the flocculation reaction surface,
There is a concern that the partial tackiness of the flock will unnecessarily increase.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction contents]

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

Example 1 Silica sand containing silicon dioxide in a high purity of about 99.8% was pulverized with a pulverizing mill so as to have a 350 mesh pass (particle diameter of about 44 μm). powder 75 wt%, 250 mesh pass about 99.8% and a high purity γ status alumina powder 20 wt%, which is milled (approximately 60μm particle diameter before and after), this made diamond flock Inc. Any one of nonionic NP800N (hereinafter abbreviated as A) or cationic KP1200B (hereinafter abbreviated as B) synthetic polymer flocculant is selected as a flocculant, and each is mixed at a ratio of 5% by weight, and a total amount of 100 g of crude Make a mixture and add one more
The mixture was uniformly pulverized and mixed with a pulverization mixer having about 3000 revolutions per minute to obtain a composition of the present invention having an average particle size of about 44 μm.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction contents]

It should be noted that the γ-form of a silica sand powder having a high purity of about 99.8% containing silicon dioxide is as high as the powder of silica sand.
The zeta potential of the mixed powder with the lumina powder when the above-mentioned predetermined amount was mixed was measured by laser Doppler electrophoresis, and the average of four measurements was minus 29.6 m.
V. As a specific measuring method, a small amount of a powder sample was put into about 30 ml of distilled water, subjected to an ultrasonic dispersion treatment for about 3 minutes, and allowed to stand for 30 minutes, and the supernatant was filtered with a 5 μm filter. It was measured after filtration. The pH value of the measurement solution is 6.
8 to 6.9. The experimental results of the embodiment of the present invention described above are as shown in Table 1 below.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction contents]

COMPARATIVE EXAMPLE 1 For comparison with the present invention, in Comparative Experimental Example 1, as a similar composition outside the scope of the present invention, a mixed powder of a silicon dioxide component and an alumina powder in the components of Example 1 was used. Example 1 was prepared in the same manner as in Example 1 except that the zeta potential was −9.4 mV as an average value of four measurements when mixing a predetermined amount as in Example 1. Experimental Example 1
The experiment was performed according to the conditions. In Comparative Experimental Example 2, an industrial commercial product, about 10% PAC solution and Diafloc 's nonionic polymer flocculant NP800N (0.1% solution) were used in combination with caustic soda solution diluted with distilled water. PH was adjusted. 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 twice with tap water. Under these conditions, a test with 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.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

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Example 2 About 80% of silicon dioxide, about 10% of alumina component,
25% of natural quartzite of about 10%
0 meshpath(Particle size of about 60μm)
The powder was crushed to obtain a blue powder. Determine the zeta potential of this powder
When checked in the same manner as in Example 1, the average
And showed minus 29.6 mV. Rock created here
90% by weight of powder and a commercially available coagulant
Rock's strong cationic synthetic polymer flocculantKP1200
BAt a ratio of 10% by weight, and a total amount of 100 g
Make a mixture and crush it for about 3000 more minutes
Pulverize and mix uniformly with a mixer, 350 meshpath
(Average particle size of about 44 μm) was obtained.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction contents]

Comparative Example 2 For comparison with the present invention, in Comparative Experimental Example 4, an experiment was conducted under the same conditions as in Experimental Example 7 of Example 2 using a similar composition outside the scope of the present invention. That is, the silicon dioxide content is about 8
A natural quartzite consisting of 0%, an alumina component of about 10% and other about 10% was pulverized by a ball mill into a 250 mesh pass (particle size of about 60 μm) to obtain a rattan powder. When the zeta potential of this powder was checked in the same manner as in Example 1, the average value was minus 10.2
mV. 90% by weight of the obtained rock powder and 10% by weight of a strong cationic synthetic polymer flocculant KP1200B from Diafloc as a commercially available flocculant were mixed at a ratio of 10% by weight, and the mixture was further mixed for about 3000 minutes for 1 minute. The mixture was uniformly pulverized and mixed with a rotary pulverization mixer to obtain a 350-mesh pass (average particle size of about 44 μm) similar composition outside the scope of the present invention.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

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On the other hand, in Comparative Experimental Example 5, an industrial commercial product was used.
About 10% PAC solution was used in combination with Diafloc 's nonionic polymer flocculant NP800N (0.1% solution), and the pH was adjusted with a sodium hydroxide solution diluted with distilled water. Further, in Comparative Experimental Example 6, experiments were performed in the same manner as Comparative Experimental Examples 2 and 3 of Comparative Example 1 except that the target raw water was diluted twice with tap water. Under these conditions, various ratios as shown in Table 4 below were added to the raw water, and a jar tester (15
(0 rpm), a flocculation test for confirming the state of floc generation was performed in the same manner as in Example 1. SS as raw water
About 1800 mg / l of oil-containing wastewater having a pH of 6.1 and having a blackish brown color was used. The evaluation was performed in the same manner as in Example 1, and the results were as shown in Table 4 below.

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

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Example 3 Quartz sand containing silicon dioxide in a high purity of about 99.8% was pulverized with a pulverizing mill so as to have a 350 mesh pass (particle size of about 44 μm). 75% by weight of the powder, 25% by weight of high-purity gamma- alumina powder of about 99.8% and milled to a 250 mesh pass (particle size of about 60 μm), and further 3,000 rpm for 1 minute Pulverized and mixed uniformly with a pulverization mixer, and the average particle size is about 44 μm
A mixed powder before and after was obtained. Zeta potential is minus 28.8
mV.

[Procedure amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction contents]

70% by weight of this mixed powder, and no
Neon NP800N (hereinafter abbreviated as A) or cationic
KP1200B (hereinafter abbreviated as B) One kind of synthetic polymer flocculant is selected and 5% by weight, and any one of commercially available bentonite powder (hereinafter abbreviated as C) or zeolite powder (hereinafter abbreviated as D) is used. Select 25% by weight and mix uniformly with a grinding mixer of about 3000 rotations for 1 minute.
100 g of each of the powdery compositions of the present invention adjusted to an average particle size of about 44 μm were obtained. All the polymer flocculants used were Diafloc products. ────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 6, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction contents]

In the present invention, a powdery flocculant composition having a specific composition can be easily obtained by simultaneously mixing the specific compounds constituting the present invention in powder form and mixing them uniformly. As the composition ratio of the composition, all of them need to correspond variably, but as a basic composition, the main component is activated silicon dioxide and alumina which are coagulant components, and the absolute value of the maximum value of the zeta potential is at least 15 mV. Preferably, it is determined by the blending amount of the powder and granules showing 20 mV and the natural or synthetic polymer flocculant. This alkali metal carbonate and / or cement powder or granular material as a pH adjusting agent, the base pairs
Calcium compound, titanium dioxide
As the third component, one selected from bentonite-based soil mineral powder or zeolite-based powder can be blended as an additive-selective substance.

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Claims (10)

[Claims] An inorganic powder containing active silicon dioxide and alumina as main components and having a maximum zeta potential of at least 15 mV in absolute value, and a water-soluble natural or synthetic polymer coagulant mixed with the inorganic powder. A powdery flocculant composition characterized by comprising: 2. The powder according to claim 1, wherein at least one selected from the group consisting of bentonite soil mineral powder and zeolite powder is added to the composition when the powdery flocculant is constituted. Body coagulant composition. 3. The powdery flocculant composition according to claim 1, wherein said active silicon dioxide comprises at least 50% by weight and said alumina comprises at least 5% by weight. 4. The powdery flocculant composition according to claim 1, wherein a nonionic or cationic natural or synthetic polymer flocculant is used as said polymer flocculant. 5. The powdery coagulant composition according to claim 1, wherein said zeta potential is at least 20 mV. 6. The natural polymer flocculant as β-1,3
The powdery flocculant composition according to any one of claims 1 to 5, wherein an acidic polysaccharide polymer mainly containing glucan is used. 7. The powder according to claim 1, wherein said powder has a particle size of at least 1
The powdery flocculant composition according to any one of claims 1 to 6, comprising a small particle size of 00 mesh under. 8. A water-soluble natural or synthetic polymer comprising 70 to 99.5% by weight of an inorganic powder mainly composed of activated silicon dioxide and alumina, wherein the composition constitutes 100% by weight of the whole composition. The powdery coagulant composition according to any one of claims 1 to 7, wherein the coagulant is uniformly mixed at 0.5 to 30% by weight to obtain a composition. 9. A water-soluble natural or synthetic polymer comprising 70 to 94.5% by weight of an inorganic powder containing activated silicon dioxide and alumina as a main component, with the composition weight ratio of the whole composition being 100%. 0.5 to 30% by weight of a flocculant,
The powdery coagulant composition according to any one of claims 1 to 8, wherein at least one selected from bentonite soil mineral powder or zeolite powder is uniformly mixed to form a composition by 5 to 30% by weight. 10. A water treatment method comprising adding the powdery flocculant composition according to any one of the above-mentioned claims to water to be treated and causing a flocculation reaction with stirring.