KR20010011572A - Coagulant composition consisting of organic coagulant of brown algae and inorganic coagulant - Google Patents

Abstract

PURPOSE: A coagulant composition containing brown algae as an organic coagulant and inorganic coagulant is provided, which is strong in coagulation and rapid in settlement, can be applied to various waste water, diminishes the amount of settled sludge, eases the secondary treatment of the sludge in the form of soft sponge, and can confirm the clearness in a few minutes by seeing. CONSTITUTION: The composition comprises the followings: (i) an inorganic coagulant component(A) containing 0.1-5wt.pts. of aluminium sulfate and more than 90wt.pts. of calcium components of shell powder, gypsum powder and calcium carbonate, the ratio of shell powder to gypsum powder being 2:8-5:5; and (ii) an organic coagulant component(B) of brown algae of tangle weed powder, the organic coagulant component(B) to the inorganic coagulant component(A) being 5-30 wt.pts.

Description

Coagulant composition containing brown algae which is an organic coagulant and an inorganic coagulant component {COAGULANT COMPOSITION CONSISTING OF ORGANIC COAGULANT OF BROWN ALGAE AND INORGANIC COAGULANT}

The present invention relates to a flocculant composition containing brown algae and an inorganic component. More specifically, it is composed of brown algae containing a small amount of one or two selected from the group consisting of shell ion powder, gypsum and calcium carbonate as an inorganic component, aluminum sulfate as an aluminum ion source and an alginate as an organic component. An inorganic / organic mixed type coagulant composition.

Agglomeration refers to the process of sedimentation and removal of impurities that cause turbidity or color of wastewater, but usually sedimentation when the turbid particles are small and do not precipitate well. Precipitation and adsorption of organic and inorganic materials of fine materials, colloidal or soluble materials are employed. Most of these chemical flocculations are used in combination with biological treatments. Aggregation removes impurities that cause turbidity such as mud particles, bacteria, algae, pigments, colloids, and organic matter. It also removes taste and odor, so it is widely used to treat contaminated surface water or various wastewater. Agglomeration is generally used as a pretreatment for precipitation or filtration. In this case, the filtration treatment is absolutely necessary, and in the case of wastewater treatment, when the filtration treatment is reused as water, the amount of solids in the filtration raw water should be reduced by effectively flocculating sedimentation in order to reduce the load of the filter. Therefore, the flocculation sedimentation method combined with flocculation and sedimentation is most frequently used in wastewater treatment because of high colloidal particle, color, BOD removal rate and fast floc sedimentation rate.

The principle of aggregation is to change the electrical properties of the colloid and reduce the ratio of surface area to weight so that sedimentation occurs easily. In other words, the fine particles containing colloidal particles suspended in water have a positive or negative charge and are repulsed due to the same kind of charge. When a substance having is added, fine flocs are formed by electrical neutralization, that is, van der Waals forces existing between the particles.

This flocculation and precipitation treatment process is the most widely used physicochemical unit process throughout the water treatment process. In general, the four mechanisms of bilayer compression, adsorption and charge neutralization, sweep aggregation, and crosslinking between particles are used. Reaction to remove contaminants is known. In particular, in the aggregation reaction using metal salts such as iron or aluminum, the adsorption and charge neutralization and sweep aggregation mechanisms are mainly used.

As the coagulant, the organic coagulant is generally divided into aluminum and aluminum, and as the inorganic coagulant, aluminum sulfate, aluminum oxide, ferrous sulfate, ferric sulfate, ferric sulfate, magnesium oxide and magnesium carbonate, and magnesium carbonate are used. Examples of the polymer flocculant include polyaluminum chloride, polyaluminum sulfate, polyferric chloride, and ferric polysulfate. Since these inorganic polymer flocculants are mostly involved in the neutralization of particle charges, it is impossible to form large flocs, the flocs formed are light and easy to float, have a narrow coagulation pH range, are highly corrosive to metals, and are expensive. Have

In addition, in the case of using an aluminum-based flocculant, aluminum may remain above the reference value after the flocculation treatment, and it is found that the remaining aluminum causes Alzheimer's disease, that is, senile dementia. It is regulated below l, and accordingly, Western countries such as Australia and the United Kingdom tend to use other metal-based flocculants instead of aluminum.

On the other hand, in the case of the organic polymer flocculant, crosslinking is formed between the particles together with neutralization to form a large floc, there is no change in pH even after the treatment, and no precipitation of the added flocculant occurs after the treatment, and the amount of generated sludge is also an inorganic flocculant. It is known to be less than that and less toxic to human body. Therefore, it is widely used for wastewater treatment which is difficult to treat only with inorganic flocculant. Such organic polymer coagulants are roughly classified into nonionic, cationic and anionic coagulants, and may be selected from various coagulants according to ionicity, degree of dissolution, effective pH range, and the like. However, such an organic polymer flocculant is very expensive and has a problem such as that it takes a long time to be activated.

As a result of intensive studies to solve the above problems, the present inventors have used aluminum-based flocculants known to be harmful to the human body in a small amount as much as possible, and mixed a large amount of shellfish, gypsum and / or calcium carbonate as calcium-based flocculants, By using inexpensive algae, especially brown algae, as a coagulant, it is possible to solve the problem of the conventional coagulant in which the aluminum component remains when a large amount of the aluminum-based coagulant is used, and can also replace the expensive organic synthetic polymer coagulant. The synthetic polymer flocculant has not been reported to have a big problem to the human body until now, but it can be expected to have more safety than the expensive organic synthetic polymer flocculant, and can greatly improve the flocculation effect. The amount is relatively very small in comparison with the conventional, soft It was found to be light in the form of a ponji so that subsequent secondary sludge treatment was easy and the present invention was completed.

That is, it is an object of the present invention to provide an inorganic / organic mixed flocculation settler composition which is inexpensive and high in flocculation efficiency, containing brown algae, without causing secondary pollution or environmental problems.

Hereinafter, the present invention will be described in detail.

1 is a view showing fine floc formation and large floc formation of particulates in waste water.

Figure 2 shows a photograph of the treatment of livestock (barn) wastewater.

The present invention is a coagulant for flocculating industrial water, various wastewater, sewage, leachate, etc., comprising an inorganic component and an organic component, the content of the aluminum component as an inorganic component within 5 parts by weight relative to the entire inorganic component of the flocculant It is to provide a flocculant composition in which the weight loss is reduced to 90 parts by weight or more, and a brown algae is used as the organic flocculant component, and 5-30 parts by weight of this is added to the inorganic component.

Moreover, you may mix | blend a well-known activated carbon, a zeolite, an elvan, etc. with the said composition according to the kind of wastewater processed. It is preferable to make these components into powder of 200 mesh or more, and, as for content of these components, 1-10 weight part is preferable with respect to a precursor, The addition of these components can be mix | blended according to a well-known method.

Conventionally, there are many kinds of flocculants used in water treatment, but most of them are formed of a single substance which is inorganic or organic, so that it is not effective to agglomerate and settle various foreign substances in the water. Therefore, a flocculation aid should be used. In addition to the difficulty and the economic burden was a disadvantage.

In order to solve this problem, the present inventors have mixed inorganic and organic components so that inorganic and organic foreign substances present in various wastewaters can be effectively and rapidly aggregated, settled, and separated to be purified. That is, the mechanism of the inorganic / organic mixed flocculant used in the present invention will be outlined as follows.

The mechanism according to the anticipated flocculation reaction path when using the inorganic / organic mixed flocculant of the present invention is considered to be the paths of the following A) and B).

Stage 1: Excess CaSO ₄ or CaCO ₃ + Al ₂ (SO ₄ ) ₃ + Positive and negatively charged foreign material

→ (adsorption) → [Al ³ +-negatively charged material with small volume] + [Ca ² +-negatively charged material with large volume] + [SO ₄ ^2- -positive charged material] + [CO ₃ ^2- -positive charged material]: ( A) pathway; Fine floc formation

Step 2: (A) + organic flocculent → (crosslinking) → (B) pathway; Greater floc formation → rapid sedimentation.

That is, as shown above, CaSO ₄ or CaCO ₃ and Al ₂ (SO ₄ ) _{3, which} are inorganic coagulants administered to wastewater and wastewater, are dissociated as Ca ¹⁺ and Al ³⁺ and SO ₄ ^{2 −} or Produces CO ₃ ^2- ions. At this time, according to the concept of small-volume / high-volume / acid / base, a larger volume of Ca ²⁺ ions has a larger volume of negative charge and a smaller volume of Al ³⁺ This small negatively charged foreign matter, and also SO ₄ ^2- ion, adsorbs and aggregates with the positively charged metal foreign matter with each other. However, the size of the floes and their density between these ions formed in step 1 are small and still remain suspended. The organic flocculents mixed together during the one-step process dissolve in water to become viscous, and the viscous organic flocculants form a strong crosslink between the small floating flocs that are secondary to each other. Heavy flocs form and settle quickly by their weight.

The above mechanism is shown in FIG.

Hereinafter, the components used in the present invention will be described in detail.

Brown algae are mentioned as an organic type flocculant used for the composition of this invention. Examples of brown algae include kelp, seaweed, and sesame. These ingredients play an important role in the clean action of the sea and are basic foods. While such seaweeds have been studied worldwide, none have been used or published as flocculant components or flocculant compositions containing them. In the present invention, as a result of intensive research on the use of such seaweeds, among the seaweeds, the red algae or the green algae alone or the flocculant composition containing the same has little or no flocculation effect. Although the use of such red algae or green algae has been described in terms of metal adsorption, it is effective to use red algae or green algae instead of brown algae in the mixed flocculant of brown algae and inorganic flocculants used in the examples of the present invention as a coagulant. It was confirmed as not shown in Table 1 below.

Note) It was used 5 times for livestock wastewater, 10 times for leachate, 50 times for slaughterwater, and 2 times for plating wastewater.

As the green algae, Jejudosan natural hearing was used, and the red algae used Jejudosan natural wood starfish. In addition, the red algae liquid was boiled in water to extract a gelled liquid. The liquid amount used was 5 ml per 10 g of each sample.

As shown in the table above, the use of green algae or red algae in place of brown algae showed little cohesive effect, and after the cutting test, the degree of purification in the treated water was reduced to COD for all wastewater except for plating waste water. Only 5-8% of raw water was lowered, COD removal rate was about 10% only for plating wastewater, and there is some possibility in heavy metal removal ability. Taken together, it is not suitable to apply green algae or red algae as flocculants.

The present invention utilizes the properties of viscous polysaccharides of brown algae, especially algin and alginic acid. These polysaccharides, along with proteins and lipids, are organic compounds that have existed on Earth for a long time and play a very important role as one of the components of animals and plants. Particularly, plant mucilages refer to polysaccharides that are dissolved in water to form a viscous solution, and are present in many algae as well as tissues of higher plants. Polysaccharides, which are the main components of seaweed, are classified into polysaccharides stored in cells (polysaccharide storage cells) and polysaccharides (cell wall component polysaccharides) constituting cell walls. Especially, polysaccharides that are soluble in water, saline solution, and alkaline solution are abundant in polysaccharides. Listen. Viscous polysaccharides of algae include various polysaccharides in addition to D-glucose, D-mannose, D-xylose, D-ribose, D-glucuronine acid, and D-galacturonic acid, and most of these polysaccharides Silver sulfate ester is contained. In particular, alginate is present in the algae as an intercellular filler in addition to the cell wall composition. The components of these alginine acids are D-mannuronic acid and D-glucuronic acid, the former is β- and the latter is α-1,4-. Linked by glucoside bonds, in fact known as heterogeneous polyglucuroninic acid mixtures, relatively stable to acid hydrolysis, sodium alginate forms a particularly viscous aqueous solution. In addition to these, fucoidan, a viscous polysaccharide present as a brown algae filling, is commonly present in the form of L-fucose-4-sulfate ester, has a 1,2-linked structure, and is located at the 3 position of some constituent sugars. The molecule of L-fucose-4-sulfate binds, and it shows structural diversity, such as containing D-xylose and D-glucuronic acid. Due to various structural properties of the viscous polysaccharides of seaweeds, seaweeds have been widely applied to electrophoretic carriers, pharmaceuticals, cosmetics, and foods.

In the flocculant composition of the present invention, the above-mentioned brown alga, that is, a powder obtained by grinding seaweed, seaweed, kelp, or the like or an extract thereof is used. In the case of using the powder, the size thereof is not particularly limited, but since the increase in the surface area has a large aggregation effect, it is preferable to use a powder of approximately 100 to 300 mesh, preferably 200 mesh or more. In addition, the extract means that the kelp or the like is extracted with water or lower alcohols such as methanol and ethanol at room temperature to 100 ° C, and such an organic component is preferably prepared at 1 to 30 parts by weight with respect to the precursor.

In addition, the inorganic flocculant component includes a calcium component and an aluminum component.

As the calcium-based component, commercially available gypsum and shells such as oysters, mussels, clams, and shellfish from which salts are pulverized by a ball mill or the like are used. Shellfish is not easy to obtain, and there are many inconveniences such as salt removal, washing, and drying, so there is no significant difference in the flocculation effect even when using gypsum and / or calcium carbonate. It is preferable to mix about 8: 2 to 5: 5. The particle size of such a calcium-based component is preferably 100 to 300 mesh. Among the calcium-based components described above, when calcium sulfate for reagents is used instead of gypsum, aggregation and sedimentation do not easily occur, even though gypsum is mainly composed of calcium sulfate. Although judged to be different by the difference, the exact aggregation and sedimentation mechanism is not clear. In addition, although calcium carbonate powder can be used instead of shellfish powder, it is preferable that it is microporous among these calcium carbonates. The gypsum powder, shellfish powder or calcium carbonate may be used only one of them, but the plating wastewater containing a large amount of heavy metals in the wastewater source is a calcium source containing a large amount of gypsum powder compared to shellfish powder or calcium carbonate. Preference is given to using.

Examples of the aluminum component include aluminum sulfate, alum and the like, and among them, inexpensive aluminum sulfate exhibits a sufficient effect, and powdered prior to compounding is used.

In addition to the above components, it is also possible to treat additives commonly used in the art, for example, activated carbon, zeolite, ganban stone powder, etc., at a temperature of 500 ° C. or lower, and pulverize to add more than 200 mesh.

EXAMPLE

Hereinafter, an Example is given and this invention is demonstrated concretely. However, the present invention is not limited by these examples.

Example 1

Collect oysters, mussels, clams and clamshells in Tongyeong, Namhae, wash them five times for 24 hours with water to remove salt, dry them, crush them first with a Jaw crusher, and then grind them secondly with a ball mill. It was crushed to obtain a powder (calcium-based raw material) of 200 mesh or more. 5 weight part of commercial aluminum sulfates were mix | blended with respect to 100 weight part of this calcium-based raw materials, and the inorganic flocculant (A) was prepared.

On the other hand, after completely drying Wando seaweed kelp, it was pulverized and passed through a 200 mesh sieve as an organic flocculant.

10 weight part of organic flocculants were mix | blended with respect to 100 weight part of said inorganic flocculants (A), and the flocculant composition 1 was obtained.

Example 2

In Example 1, 5 parts by weight of the organic flocculant was blended with respect to 100 parts by weight of the inorganic flocculant (A) to prepare a flocculant composition 2.

Example 3

In the said Example 1, the flocculant composition 3 was prepared like Example 1 except having used the mixture of shellfish powder (200 mesh passage) and gypsum powder as 2: 8 as a calcium source among inorganic flocculants.

Example 4

In the said Example 1, the flocculant composition 4 was prepared like Example 1 except having used the mixture of gypsum powder and calcium carbonate powder 5: 5 as a calcium source among inorganic flocculants.

Example 5

Collect shellfish fossils from Jeju Island, wash them five times with water for 24 hours to remove salt, dry them, crush them first with a jaw crusher, crush them secondly with a ball mill, and crush them to grind powders of 200 mesh or more. Got it. 4 times of gypsum powder was mixed with this powder, and it was set as the calcium type inorganic coagulant. 5 weight part of commercial aluminum sulfates were mix | blended with respect to 100 weight part of this calcium-based raw materials, and the inorganic flocculant (A) was obtained.

On the other hand, after completely drying Wando seaweed kelp, it was pulverized and passed through a 200 mesh sieve as an organic flocculant.

30 weight part of organic flocculants were mix | blended with respect to 100 weight part of said inorganic flocculants (A), and the flocculant composition 5 was prepared.

Test Example

<Test Methods>

Various wastewaters were tested by the Jar Test (aggregation test).

In order to suppress the change of the characteristics of the wastewater sample for the aggregation and sedimentation experiment, it was cooled to 4 ° C. In addition, six 1000 ml beakers were simultaneously operated using a Jar tester known in the art. Unlike conventional test methods, rapid stirring (100 rpm) was performed for 1 minute, allowed to stand for 3 minutes, and COD _Mn , SS (Supended Solid), Turbidity (Turbidity) and the like were analyzed. In the conventional test method, rapid stirring at 100 rpm for the first 3 to 5 minutes of stirring and slow stirring at 40 to 50 rpm for the next 10 to 15 minutes is allowed to stand for about 1 hour, and the turbidity, chromaticity, and pH of the supernatant are maintained. In the case of using the flocculant composition of the present invention, the flocculation and precipitation occur as soon as the flocculant is added. In the comparative example, however, as the conventional flocculating flocculant does not rapidly aggregate and precipitate like the flocculant of the present invention, similarly to the conventional test method, the first one minute is rapidly stirred at 100 rpm and the next one minute is 50 rpm. After slow stirring, the mixture was allowed to stand for about 5 minutes and subjected to various tests.

The flocculation effect according to the amount of flocculant for each wastewater was adjusted to each condition, and then cut tests were carried out three times for each flocculant, and the average values are shown in tables in the respective test examples.

Test Example 1 (Agglomeration Effect of Barn Wastewater)

Table 2 shows that the first strained wastewater obtained from the barn obtained from farms in Hwaseong, Gyeonggi-do was cut and tested using the flocculant composition 1 of Example 1.

In Table 2, the dilution rate of raw wastewater to raw water was 5 times, and the flocculant amount "0" is the result of undiluted raw water itself.

When the amount of flocculant was used 3 to 5 g, the flocculation effect was the highest, and the reduction effect of COD over the entire range was 87-90%. SS was almost absent, and the total nitrogen was also remarkably decreased compared to the raw water. At this time, the pH was slightly lower depending on the amount of flocculant added, showing almost neutrality. The wastewater before treatment was very turbid, brownish, and had a bad odor. However, after the addition of the flocculant, the wastewater rapidly aggregated for about 1 minute. After stopping the agitation and observing with eyes, the solution precipitated completely clear and was a pale yellow solution of almost colorlessness and almost no smell. This test procedure is shown in FIG.

* 1: Measured using Mn oxidation method.

* 2: Larger value is better

* 3: Volume injected by injection into a 1000 ml measuring cylinder

* 4: Measured after 24 hours drying

* 5: Measured using an ultraviolet absorbance photometer.

Test Example 2 (Agglomeration Effect of Piglet Wastewater)

It was shown in Table 3 that the primary strained pig wastewater obtained from Chungbuk J city was cut-tested using the flocculant composition 2 of Example 2.

In Table 3, the dilution rate for the raw water of pig wastewater was 10-fold, and the flocculant amount "0" is the result of undiluted raw water itself.

When the amount of flocculant was used 5-7 g, the flocculation effect was the highest, and the reduction effect of COD over the entire range was 82-87%. SS was almost absent, and the total nitrogen was also remarkably decreased compared to the raw water. At this time, the pH was slightly lower depending on the amount of flocculant added, showing almost neutrality. The wastewater before treatment was very turbid, brownish, and had a bad odor. However, after the addition of the flocculant, the wastewater rapidly aggregated for about 1 minute. After stopping the agitation and observing with eyes, the solution precipitated completely clear and was a pale yellow solution of almost colorlessness and almost no smell.

* 1: Measured using Mn oxidation method.

* 2: Larger value is better

* 3: Volume injected by injection into a 1000 ml measuring cylinder

* 4: Measured after 24 hours drying

* 5: Measured using an ultraviolet absorbance photometer.

Test Example 3 (Agglomeration Effect of Garbage Leachate)

Table 4 shows that the leachate without any treatment obtained in Chungbuk J city was cut-tested using the flocculant composition 4 of Example 4.

In Table 4, the dilution ratio of the leachate to the raw water was 10 times, and the flocculant amount "0" is the result of undiluted raw water itself.

When the amount of flocculant was used 3 to 5 g, the flocculation effect was the highest, and the reduction effect of COD over the entire range was about 80 to 84%. SS was hardly shown below 10 ppm, and the total nitrogen was also remarkably decreased compared to the raw water. At this time, the pH was slightly lowered according to the amount of flocculant added, showing almost neutrality. Before treatment, the wastewater was very turbid, dark blue, and had a bad odor, resulting in headache and vomiting. However, after the addition of flocculants, the wastewater rapidly aggregated. After stopping the agitation and observing with the eyes, it was completely clear, and it was a pale green solution of almost colorlessness and almost no smell.

* 1: Measured using Mn oxidation method.

* 2: Larger value is better

* 3: Volume injected by injection into a 1000 ml measuring cylinder

* 4: Measured after 24 hours drying

* 5: Measured using an ultraviolet absorbance photometer.

Test Example 4 (Agglomeration Effect of Dyeing Wastewater)

Table 5 shows the results of testing the raw wastewater from untreated treatment obtained in Chungnam C City using the flocculant composition 5 of Example 5.

When the amount of flocculant was used 7 to 15 g, the flocculation effect was the highest, and the reduction effect of COD over the entire range was 92-95%. SS was hardly shown below 10 ppm, and the total nitrogen was also remarkably decreased compared to the raw water. At this time, the pH was slightly lowered according to the amount of flocculant added, showing almost neutrality. The condition of the wastewater before treatment was very turbid and grey, but the smell was not so bad. After the addition of the flocculant, about 1 minute elapsed, a phenomenon of rapidly agglomeration was observed. The stirring was stopped and after a few minutes, when visually observed, it settled completely clear and became a colorless transparent solution.

* 1: Measured using Mn oxidation method.

* 2: Larger value is better

* 3: Volume injected by injection into a 1000 ml measuring cylinder

* 4: Measured after 24 hours drying

* 5: Measured using an ultraviolet absorbance photometer.

Test Example 5 (Agglomeration Effect of Slaughter Wastewater)

Table 6 shows the raw slaughtered raw water obtained from Chungbuk J City, which was tested using the flocculant composition 3 of Example 3.

The dilution rate for slaughter wastewater was 50 times, and the flocculant amount "0" was the result of undiluted raw water itself.

When the amount of flocculant was used 15 to 20 g, the flocculation effect was the highest, and the reduction effect of COD over the entire range was about 80 to 83%. SS was hardly shown below 10 ppm, and the total nitrogen was also remarkably decreased compared to the raw water. At this time, the pH was slightly lowered according to the amount of flocculant added, showing almost neutrality. Before treatment, the wastewater was very turbid and dark red in color and had a bad smell. After stirring was stopped and after a few minutes, when visually observed, the solution was completely cleared and became a pale yellow transparent solution that was almost colorless. The smell is almost gone.

* 1: Measured using Mn oxidation method.

* 2: Larger value is better

* 3: Volume injected by injection into a 1000 ml measuring cylinder

* 4: Measured after 24 hours drying

* 5: Measured using an ultraviolet absorbance photometer.

Test Example 6 (Agglomeration Effect of Hospital Wastewater)

Table 7 shows a test using the flocculant composition 2 of Example 2 for untreated wastewater raw water obtained from Chungbuk H Hospital.

When the amount of flocculant was used 3-7 g, the flocculation effect was the highest, and the COD reduction effect was 83-88% over the whole range. SS was hardly shown below 10 ppm, and the total nitrogen was also remarkably decreased compared to the raw water. At this time, the pH was slightly lowered according to the amount of flocculant added, showing almost neutrality. Before treatment, the wastewater was very turbid and gray and had a bad smell. However, after the addition of the flocculant, the wastewater rapidly aggregated for about 1 minute. After agitation was stopped and a few minutes later, when visually observed, the solution completely settled out to a colorless transparent solution.

* 1: Measured using Mn oxidation method.

* 2: Larger value is better

* 3: Volume injected by injection into a 1000 ml measuring cylinder

* 4: Measured after 24 hours drying

* 5: Measured using an ultraviolet absorbance photometer.

Test Example 7 (Coagulation Effect of Plating Wastewater)

Table 8 shows the test of the plating wastewater raw water obtained from M company, an accessory manufacturer of Gyeonggi-do, using the flocculant composition 4 of Example 4.

The dilution ratio of the plating wastewater to the raw water was doubled, and the flocculant amount "0" is the result of undiluted raw water itself.

When the amount of flocculant was used 3 to 5 g, the flocculation effect was the highest, and the reduction effect of COD over the entire range was 93-97%, which was very high. SS was hardly shown below 10 ppm, and the total nitrogen was also remarkably decreased compared to the raw water. At this time, the pH was slightly lowered according to the amount of flocculant added, showing almost neutrality. Before treatment, the wastewater was very turbid and gray and had a bad smell. However, after the addition of the flocculant, the wastewater rapidly aggregated for about 1 minute. After agitation was stopped and a few minutes later, when visually observed, the solution completely settled out to a colorless transparent solution.

* 1: Measured using Mn oxidation method.

* 2: Larger value is better

* 3: Volume injected by injection into a 1000 ml measuring cylinder

* 4: Measured after 24 hours drying

* 5: Measured using an ultraviolet absorbance photometer.

Test Example 8 (Heavy metal removal test for various wastewater)

As a result of the Zar test, a comparison of the heavy metals contained in raw water and treated water obtained from Inductively Coupled Plasma Atomic Emission Spectrometry (ICP) is shown in Table 9 below. All values represent the results under the best conditions for each wastewater.

As shown in Table 9, the coagulation effect on the heavy metals was excellent in most wastewaters, especially in the livestock wastewater, the removal rate of total phosphorus was higher than 95%, and also showed a large removal rate for other heavy metals. In the case of pig wastewater, it can be seen that most heavy metals including phosphorus are aggregated and removed, and the iron and aluminum contents in the treated water are hardly present. In the case of leachate, total phosphorus removal rate was very high and the contents of manganese and iron including zinc were greatly reduced. In the case of the dyeing wastewater, aluminum and iron had good effects, but in the case of lead and manganese, there was almost no difference in raw water.

In the case of slaughter wastewater, the removal rate of total phosphorus was surprisingly high, showing a high removal rate for most metals such as iron, zinc and aluminum. In the case of hospital wastewater, it showed effects such as zinc, iron, and aluminum, and in the case of plating wastewater, high removal rate was shown in lead including zinc. As such, most of the wastewater has removed high levels of heavy metals that are a concern for environmental standards.

Example 6 (Agglomeration effect when the mixing ratio of the flocculant is different for the barn wastewater) Using the flocculant of the mixing ratio of the calcium source, aluminum sulfate and kelp powder shown in Table 10, was tested in accordance with the method of Test Example 1, the supernatant Taking the COD, SS, phosphorus, nitrogen content was measured, and the results are shown in Table 10 together.

Note) In the table, the calcium source is a mixture of 90 parts by weight of gypsum and 10 parts by weight of shellfish powder described in Example 1, the kelp powder is the same as that used in Example 1, and aluminum sulfate is used as a commercial flocculant.

^{1 *} , ^{2 *} , ^{4 *} : The larger the value, the better.

^{3 *} : The smaller the value, the better.

It can be seen from the table that the mixing ratio of the weight ratio of aluminum sulfate: calcium source: tangle powder = 0.3 to 0.75: 7.5 to 10.0: 0.75 to 1.5 of the flocculant to the barn wastewater is optimal.

Example 7 (Agglomeration Effect with Different Mixing Ratio of Coagulant to Leachate)

Tested according to the method of Test Example 1 using a flocculant of the mixing ratio of the calcium source, aluminum sulfate and kelp powder shown in Table 11 below, taking the supernatant to measure the COD, SS, phosphorus, nitrogen content, and the results are shown in Table 11 It is described together in.

Note) In the table, the calcium source is a mixture of 50 parts by weight of gypsum and 50 parts by weight of shellfish powder described in Example 1, the kelp powder is the same as that used in Example 1, and aluminum sulfate is used as a commercial flocculant.

^{1 *} , ^{2 *} , ^{3 * 4 *} : same as Example 6

It can be seen from the table that the mixing ratio of aluminum sulfate: calcium source: kelp powder = 0.3 to 0.75: 10.0 to 12.5: 1.0 to 1.5 of the flocculant to the leachate wastewater is optimal.

Example 7 (Agglomeration Effect with Different Mixing Ratio of Coagulant to Slaughter Wastewater) Test was carried out according to the method of Test Example 1 using a coagulant of the mixing ratio of calcium source, aluminum sulfate and kelp powder shown in Table 12 below, and the supernatant liquid. Taking the COD, SS, phosphorus, nitrogen content was measured, and the results are shown in Table 12 together.

Note) In the table, the calcium source is a mixture of 50 parts by weight of gypsum and 50 parts by weight of shellfish powder described in Example 1, the kelp powder is the same as that used in Example 1, and aluminum sulfate is used as a commercial flocculant.

^{1 *} , ^{2 *} , ^{3 * 4 *} : same as Example 6

It can be seen from the above table that the mixing ratio of the aluminum sulfate: calcium source: tangle powder of kelp powder = 0.5 to 0.75: 10.0 to 15.0: 1.5 to 2.0 is optimal for slaughter wastewater.

Example 8 (Agglomeration effect when the mixing ratio of the flocculant was changed with respect to the plating waste water) Using the flocculant of the mixing ratio of the calcium source, aluminum sulfate and kelp powder shown in Table 13, was tested in accordance with the method of Test Example 1, the supernatant Taking the COD, SS, phosphorus, nitrogen content was measured, and the results are shown in Table 13 together.

Note) In the table, the calcium source is a mixture of 90 parts by weight of gypsum and 10 parts by weight of calcium carbonate. The kelp powder is the same as that used in Example 1, and aluminum sulfate is used as a commercial flocculant.

It can be seen from the above table that the mixing ratio of aluminum sulfate: calcium source: kelp powder = 0.3 to 0.5: 7.5 to 10.0: 0.75 to 1.5 of the flocculant to the plating wastewater is optimal.

Example 9 (Agglomeration Effect When Using Kelp Extract as Organic Coagulant for Various Wastewaters) Test was conducted according to the method of Test Example 1 using a coagulant having a mixing ratio of calcium source, aluminum sulfate and kelp extract shown in Table 14 below. The supernatant was taken, and the COD, SS, phosphorus, and nitrogen contents were measured, and the results are shown in Table 14 together.

week)

1) In the table, kelp liquor, which is a brown algae source, was obtained by immersing 100 g of naturally dried kelp in 2 liters of distilled water for 24 hours.

2) In the table, the calcium source of livestock wastewater (dilution rate 5 times) is a mixture of 90 parts by weight of gypsum and 10 parts by weight of waste shellfish powder. The calcium source of leachate (10 times of dilution rate) is 50 parts by weight of gypsum and waste shellfish powder. 50 parts by weight of a mixture of 50% by weight of gypsum and 50 parts by weight of waste shellfish powder was mixed with calcium source of slaughter wastewater (dilution rate of 50 times), and 90% by weight of gypsum and carbonic acid of plating waste water (dilution rate of 2 times). 10 parts by weight of calcium is mixed.

3) In the table, the weight of calcium source and aluminum sulfate are fixed at the optimum conditions and only the amount of kelp solution is considered.

4) ^{1 *} , ^{2 *} , ^{3 *} : The larger the value, the better.

5) ^{4 *} : The smaller the value, the better.

As shown in the table above, when kelp liquor is used as the brown algae source, the liquid amount is 3 to 5 ml for livestock wastewater, 5 to 7 ml for leachate, 7 to 10 ml for slaughter, and plating wastewater. Strong agglomeration was observed in the range of 5-7ml, COD and SS values were removed around 90% over the entire range, and the removal rate was increased by 2-4% compared to the case of using kelp powder. In addition, the metal removal ability was slightly increased compared to the powder. In particular, compared to the case of using kelp powder, the flocculation speed was slightly higher (agglomeration occurred almost simultaneously with addition), and the transparency of the treated water became clearer. In the case of using the kelp extract, there is also the above-mentioned advantages, but after adding a calcium source and an aluminum source and rapidly stirring for 1 minute, there is a hassle to add the kelp extract and rapidly stirring for 1 minute and then to stand still. There are also disadvantages that increase the economic burden.

Comparative test example 1

Coagulation effect was measured using 5 g each of alum, polyaluminum chloride (PAC), and flocculant 3 of Example 3 of the present invention with respect to the livestock (barn) wastewater, and the results are shown in Table 15 below. Polyaluminum chloride was used dissolved in water 24 hours ago.

Note) ^{1 *} , ^{2 *} , ^{3 *} : The larger the value, the better

As shown in the table above, when alum is used as a flocculant, the COD removal rate is about 60%, about 30% for SS, phosphorus and nitrogen, and about 70% for PAC, and about SS and phosphorus. For nitrogen, the removal rate is about 40%, but when the flocculant of the present invention is used, the removal rate is 90% or more for each.

Comparative Test Example 2

Coagulation effect was measured using 5 g of alum, polyaluminum chloride (PAC), and flocculant 2 of Example 2 of the present invention with respect to leachate, respectively, and the results are shown in Table 16 below.

Note) ^{1 *} , ^{2 *} , ^{3 *} : The larger the value, the better.

As shown in the table above, when alum is used as a flocculant, the COD removal rate is about 60%, about 40% for SS, phosphorus and nitrogen, and about 70% for PAC, and about SS and phosphorus. For nitrogen, the removal rate is about 60%, but when the flocculant of the present invention is used, the removal rate is 90% or more for each.

Comparative Test Example 3

Coagulation effect was measured using 5 g each of alum, polyaluminum chloride (PAC), and flocculant 4 of Example 4 of the present invention with respect to the plating wastewater, and the results are shown in Table 17 below.

As shown in the table above, when alum is used as a flocculant, the COD removal rate is about 60% for SS, phosphorus, and nitrogen, and about 60% for PAC, and about 70% for SS, phosphorus, and nitrogen. For nitrogen, the removal rate is about 70%, but when using the flocculant of the present invention, the removal rate is 90% or more for each.

As described above, in the case of treating various wastewaters using the flocculant of the present invention, the cohesiveness of foreign substances in the water is stronger than the conventional single flocculant, the sedimentability is very fast, and the coagulation range is wide, so that it can be applied to various wastewater. The size of the flocculated particles is considerably large, and the amount of precipitated sludge is considerably less than that of the conventional flocculant, and is light in the form of a soft sponge to facilitate subsequent secondary sludge treatment. In particular, raw water turbidity can be confirmed by clear observation within a few minutes after permeation of the flocculant, and also shows an excellent effect even if the amount of flocculant used is small. In particular, since the aluminum content in the treated water is very low, the problems caused by this can be solved. Furthermore, since the treated water becomes neutral and does not need to be neutralized with acid or alkali, it provides a useful invention that can reduce the economic burden of secondary treatment.

Claims (9)

1) an inorganic flocculant component (A) containing an aluminum component and a calcium component; 2) Organic substance flocculant component (B) which is brown algae Flocculant composition consisting of. The flocculant composition according to claim 1, wherein the inorganic flocculant component (A) is composed of 0.1 to 5 parts by weight of the aluminum component and 90 parts by weight or more of the calcium component. The composition according to claim 1 or 2, wherein the aluminum component is aluminum sulfate. The composition according to claim 1 or 2, wherein the calcium-based component is at least one selected from the group consisting of shellfish powder, gypsum powder and calcium carbonate. The composition according to claim 1 or 2, wherein the calcium-based component is gypsum powder. The composition according to claim 5, wherein the calcium-based component is a mixture of shellfish powder and gypsum powder in a ratio of 2: 8 to 5: 5. The composition according to claim 1, wherein the brown algae, which is an organic flocculant, is kelp powder or an extract thereof. The composition according to claim 1 or 2, wherein 5 to 30 parts by weight of the organic coagulant component (B) is blended with respect to the inorganic coagulant component (A). The composition according to claim 8, wherein the organic flocculant is kelp powder or kelp extract.