KR102254568B1 - Preparation method for flocculant composition for treating wastewater with improved water treatment efficiency and stability - Google Patents

Abstract

The present invention relates to a method of preparing a coagulant composition for water treatment with improved water treatment efficiency, and in the case of a coagulant prepared by the method according to the present invention, floc formation is formed even when a small amount is added compared to commonly used polyaluminum chloride and aluminum sulfate. It is larger and harder than this and can improve water treatment efficiency.At the same time, it can significantly lower the dissolution as well as particulate SS and turbidity in wastewater containing dissolved phosphorus, nitrogen, fluorine, etc., and reduce the volume of sludge to enable stable water treatment. In addition, there is an advantage in that water treatment efficiency is very excellent and stability is remarkably improved even when inflow of algae.

Description

Preparation method for flocculant composition for treating wastewater with improved water treatment efficiency and stability}

The present invention relates to a method for producing a coagulant composition for water treatment having excellent water treatment efficiency and stability, a coagulant composition prepared according to the production method, and a water treatment method using the same.

When solid particles or the like are present in water, the process of removing and/or separating these particles is used in various fields such as food and chemical industries as well as water treatment industry. In particular, coagulation and precipitation processes are used in many processes such as sewage and wastewater treatment, water purification, groundwater treatment, red tide removal, purification of contaminated soil treated water, treatment of contaminated water such as lake purification, and production of industrial/agricultural/potable water. Recently, as environmental pollution has emerged as a social problem, development of a coagulant that exhibits excellent efficacy in removing pollutants is required.

In general, high-basic coagulants are known to have a large and hard floc compared to general coagulants, so that the sedimentation speed is high, so that the water treatment efficiency is excellent. have. However, in the case of a high-basic coagulant, it is very excellent in removing turbidity and SS, but there is a problem that it cannot be treated in sewage or wastewater containing a lot of dissolved phosphorus, nitrogen, and fluorine, not particulate colloids.

Therefore, in sewage and wastewater treatment plants containing a lot of dissolved phosphorus, nitrogen, and fluorine, aluminum sulfate and polyaluminum polychloride are widely used. However, this is effective in removing dissolved phosphorus, nitrogen, and fluorine when inflow of dissolved sewage and wastewater, but there is a problem that SS and turbidity are not removed. In addition, when raw water containing a lot of particulate phosphorus, nitrogen, fluorine, etc. is introduced, there is a problem that it is not possible to treat not only SS, turbidity, phosphorus, nitrogen and fluorine. In particular, aluminum sulfate is a monomolecular coagulant, which has the advantage of being inexpensive, but has a disadvantage in that it has a lower coagulation effect than a polymer coagulant, and that the alkalinity and pH of the treated water after treatment are largely lowered.

Until now, there is no coagulant that can treat both particulate and dissolved properties, and in the case of sewage and wastewater treatment plants, the properties of raw water are easily changed, and thus, there are many difficulties in water treatment. In addition, in the case of sewage and wastewater treatment plants, sludge is returned to maintain MLSS (mixed liquer suspended solid) for biological treatment, and when the amount of sludge returned is increased or the water treatment efficiency is low, the sludge interface is high, resulting in a phenomenon in which fin flocs are floated. There is this.

On the other hand, hydrofluoric acid is a material used in the display and semiconductor industries, and is highly toxic and corrosive. In particular, the amount used in the surface treatment and etching process continues to increase. Since hydrofluoric acid is used in different concentrations depending on the process used and the types of chemicals used together, the generated wastewater also has different properties, and in general, the concentration of fluorine ions in the wastewater generated in the glass etching process is 500~2,000 mg/ The concentration change is large about L, and it exists in a relatively high concentration. Fluoride is an element that causes fatal toxicity when its value exceeds 5 mg/L, and the concentration of fluorine in industrial wastewater is regulated as a management item that must be carefully managed and treated.

The most commonly used method to remove fluorine is a cohesive precipitation process that forms a _{poorly soluble CaF 2} precipitate using calcium components such as slaked lime and calcium chloride. However, in some processes, the fluoride borates (BF ^4- ) generated by the reaction of the boron compound and F- do not react with calcium ions, so treatment efficiency is low, and thus, there are many difficulties in removing total fluorine. If fluoride borate is contained in wastewater, fluoride borate remains even after chemical treatment with slaked lime, acting as a cause of exceeding the allowable fluorine emission standard. In general, fluoride borate is decomposed using aluminum to remove total fluorine, but fluoride borate decomposition is processed by decomposing fluoride borate into fluorine at low pH and high water temperature.

The mechanism of formation and removal of fluoroborate is as follows:

Reaction of the fluoride ion and a calcium ^{ion: Ca 2+ + 2F - = CaF} 2 ↓

Fluorine ions react with calcium ions to form poorly soluble calcium fluoride and are removed in the form of precipitates.

Accordingly, the improved form of coagulant enables stable water treatment by lowering the height of the sludge interface during sewage/wastewater treatment by reducing the volume of sludge and improving turbidity while having excellent removal effect of dissolved phosphorus, nitrogen, fluorine and SS. Is necessary.

Throughout this specification, a number of papers and patent documents are referenced and citations are indicated. The disclosure contents of the cited papers and patent documents are incorporated by reference in this specification as a whole, and the level of the technical field to which the present invention belongs and the contents of the present invention are more clearly described.

Korean Patent Registration No. 1,409,870 (registered on June 13, 2014) Korean Patent Registration No. 1,374,191 (registered on March 7, 2014) Korean Patent Registration No. 1,661,179 (registered on September 23, 2016) Japanese Patent No. 4,136,107 (registered on August 13, 2001) Korean Patent Registration No. 1,101,760 (registered on December 27, 2011) Korean Patent Registration No. 735,540 (registered on July 28, 2001)

Seung-Woo Han et al., Physical Effects on the Manufacturing of Al(III)-based Inorganic Polymer Coagulant for Water Treatment, Journal of Chemical Engineering, Vol. 42, No. 5, Vol. 226, pp. 612-618 (2004. 10) Kang-Seok Geum, A Study on the Characteristics Comparison and Injection Rate of PAC and LAS, Coagulant for Water Treatment, Chonnam National University Master's Thesis (1997) Hyungjin Kim, Developed and commercialized high-functional aluminum-based flocculant for water treatment, Commax Chemical (2012)

In the present invention, in the treatment of water purification, sewage and wastewater, dissolved phosphorus, nitrogen, and fluorine as well as particulate suspended solids (SS) can be removed, and a method for preparing a stable coagulant while improving turbidity and such a method It is an object of the present invention to provide a method for improving water treatment efficiency by providing a coagulant composition prepared according to the present invention and applying it.

In addition, in the present invention, it is an object of the present invention to provide a method for stable water treatment by lowering the height of the sludge interface during sewage and wastewater treatment by minimizing the sludge volume by having superior sedimentation properties than the currently commercially available inorganic coagulants. .

In addition, the present invention is applied in various ways to sewage and wastewater treatment, and the floc formation is larger and harder than that required when using a commonly used coagulant polyaluminum chloride, aluminum sulfate, etc. It is an object of the present invention to provide a method of improving efficiency and significantly reducing water treatment costs.

Other objects and advantages of the present invention will become more apparent by the following detailed description, claims and drawings.

In the case of the polychlorinated aluminum silicate coagulant prepared according to the manufacturing method of the present invention, the floc formation is larger and harder even when a small amount is added compared to commonly used polyaluminum chloride and aluminum sulfate, so that water treatment efficiency can be improved. At the same time, in wastewater containing dissolved phosphorus, nitrogen, and fluorine, it is possible to significantly lower the dissolution as well as particulate SS and turbidity.Stable water treatment is possible by reducing the volume of sludge, and the water treatment efficiency is very excellent even when inflow of algae. The present invention was completed by newly discovering that there is an advantage in that stability is remarkably improved.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a method for producing polychlorinated aluminum silicate, and more particularly, (a) aluminum hydroxide (Al(OH) ₃ ) 15 to 25% by weight and 20 to 40% by weight of aluminum oxide 40 to 70% by weight. Mixing 50 to 75% by weight of hydrochloric acid and 10 to 35% by weight of water to prepare aluminum chloride having 9 to 17% by weight of aluminum oxide and 0.1 to 25% of basicity;

(b) aluminum oxide 40 to 70% by weight of aluminum hydroxide (Al(OH) ₃ ) 8 to 15% by weight, 60 to 98% by weight of sulfuric acid 12 to 30%, water 60 to 80% by weight of aluminum oxide 5 Preparing aluminum sulfate with ~9% by weight and 10-30% by weight of sulfate ions;

(c) 10-30% by weight of NaOH having a concentration of 10-50% by weight of sodium oxide (Na2O) is added to 70-90% by weight of the mixture obtained in step (b), or 50- Adding 10 to 50% by weight of sodium aluminate to 90% by weight and reacting at a temperature of 50 to 200°C to prepare a basic aluminum sulfate having 3 to 8% by weight of aluminum oxide and 10 to 27% by weight of sulfate ions;

(d) 60 to 85% by weight of the mixture obtained in step (a) and 15 to 40% by weight of the basic aluminum sulfate obtained in step (c) are mixed and reacted at a temperature of 100 to 200°C to 8 to 14 weight of aluminum oxide %, preparing an aluminum chloride sulfate having a basicity of 15 to 40%; And

(e) 10 to 25% by weight of sodium aluminate _{with a sodium oxide (Na 2} O) concentration of 10 to 40% by weight, aluminum oxide (Al ₂ O ₃ ) concentration of 15 to 30% by weight in 35 to 80% by weight of aluminum chloride sulfate, 10 to 40% by weight sodium silicate or 10 to 40% by weight sodium aluminum silicate or 10 to 70% by weight zeolite 0.1 to 10% by weight and 7 to 40% by weight of water 5,000 to 20,000 rpm at a temperature of 30 to 100 °C It includes the step of mixing and reacting at a rate of.

By the method according to the present invention, aluminum polychlorinated sulfate aluminum silicate represented by the following formula (1) can be prepared:

[Formula 1]

Al _a (OH) _b Cl _c (SO ₄ ) _d (SiO ₂ )

In the above formula,

6≤a≤10, 9≤b≤21, 3≤c≤13, d≤1.

Here, 10 to 40% sodium silicate or 10 to 40% sodium aluminum silicate or 10 to 70% zeolite 0.1 to 10% by weight and 7 to 40% by weight of water are used in the steps (a), (b), ( c), or (d), or (e) may include a step of reacting by adding it to any one of the steps.

In one aspect of the present invention, in Formula 1, when a=6, 9≤b≤13, 3≤c≤7, d≤1; when a=7, 10≤b≤15, 4≤c≤9, d≤1; when a=8, 12≤b≤17, 5≤c≤10, d≤1; when a=9, 13≤b≤19, 6≤c≤12, d≤1; Alternatively, when a=10, 15≤b≤21, 7≤c≤13, and d≤1 may be.

In one aspect of the present invention, in Formula 1, a=6, b=11, c=5, d≤1, or a=7, b=13, c=6, and d≤1 Can be

In one aspect of the present invention, the obtained aluminum silicate polychloride sulfate has _{a concentration of Al 2} O ₃ of 10 to 19% by weight, a basicity of 50 to 75%, and a chloride (Cl) of 10 to 20% by weight, , (SO ₄ ) ^2- is 0.1 to 5% by weight, and SiO ₂ may be 0.01 to 2% by weight.

In one aspect of the present invention, the obtained aluminum silicate polychloride sulfate has _{a concentration of Al 2} O ₃ of 10% by weight or more and less than 19% by weight, a basicity of 50% or more and less than 70%, and a chloride (Cl) of 10 It may be ~20% by weight, (SO ₄ ) ^2- is 0.5 to 4.0% by weight, and SiO ₂ may be more than 0.01% by weight and 2% by weight or less.

In one aspect of the present invention, the obtained aluminum silicate polychloride sulfate has _{a concentration of Al 2} O ₃ of 10 to 18% by weight, a basicity of 50 to 68%, and a chloride (Cl) of 10 to 20% by weight, , (SO ₄ ) ^2- is 0.7 to 4.0% by weight, and SiO ₂ may be 0.015 to 1.5% by weight.

In one aspect of the present invention, the polychlorinated aluminum silicate-based flocculant is more specifically, 1) _{the concentration of Al 2} O ₃ is 10 to 19% by weight, 10 to 19% by weight, 10 to 18% by weight, 10 to 17% by weight, 10 to 16% by weight, 10 to 15.5% by weight, 10 to 15% by weight, 10 to 14% by weight, 10 to 13% by weight, may be 10 to 12% by weight; 2) Basicity 50-75%, 50-74%, 50-73%, 50-72%, 50-71%, 50-70%, 50-69%, 50-68%, 50-67%, 50 It can be ~66%, 50~65%, 50~64%, 50~63%, 50~62%, 50~61%, 50~60%, where the upper limit of each basicity is less than that value, or May be less than that number; 3) chloride (Cl) may be 10 to 20% by weight, 10 to 19% by weight, 10 to 18% by weight, 10 to 17% by weight, 10 to 16% by weight, 10 to 15% by weight; 4) (SO ₄ ) ^2- This is 0.1~5 wt%, 1~4.9 wt%, 1~4.8 wt%, 1~4.7 wt%, 1~4.6 wt%, 1~4.5 wt%, 1~4.4 wt% , 1 to 4.3% by weight, 1 to 4.2% by weight, 1 to 4.1% by weight, 1 to 4.0% by weight, 0.5 to 4.0% by weight, 0.7 to 4.0% by weight, and _{the lower limit of (SO 4} ) ^2- is 0.1% by weight %, 0.5%, 0.7%, 1%, 1.1%, 1.2%, 1.3%, 1.4% or 1.5% by weight; 5) SiO ₂ is 0.01 to 2% by weight, more than 0.01% by weight and 2% by weight or less, 0.015 to 2% by weight, 0.015 to 1.5% by weight, 0.1 to 2% by weight, 0.5 to 1.5% by weight, 1 to 1.5% by weight I can.

Polychlorinated aluminum silicate manufactured according to the method according to the present invention, when _{the concentration of Al 2} O ₃ , basicity, chloride concentration, (SO ₄ ) ^2- and SiO ₂ is within the above range, the dissolution property Removal of phosphorus, nitrogen, fluorine and suspended solids (SS); Turbidity improvement; And the sludge volume reduction effect is the most excellent. If it is less than the lower limit, the desired level of effect is not expressed, and if it exceeds the upper limit, the effect is insignificant, or there is a problem in that stability is not secured during manufacture.

The polychlorinated aluminum silicate-based flocculant prepared by the method according to the present invention maintains excellent flocculation performance, has excellent stability, such as no precipitation of solid precipitates during long-term storage periods, as well as soluble phosphorus, nitrogen, and fluorine. In addition, by removing suspended solids (SS), improving turbidity, and minimizing sludge volume, stable water treatment is possible by lowering the height of the sludge interface during sewage and wastewater treatment.

The polysulphate aluminum silicate is a URC (Ultra Rapid Coagulation) method, A2O (Anaerobic Anoxic Aerobic) method, MLE (Modified Ludzack-Ettinger) method, MRB (Membrane Bioreactor) method, SBR (Sequencing Batch) method of sewage and wastewater treatment processes. Reactor) method, BARDENPHO method, and DNR (Daewoo Nutrient Removal) method.

In yet another aspect of the present invention, there is provided a coagulant composition for water purification and sewage/wastewater treatment, comprising aluminum polychloride sulfate aluminum silicate prepared by the above method.

In yet another aspect of the present invention, comprising the step of treating a coagulant containing the polychlorinated aluminum silicate in contaminated water, and as the treatment, dissolved phosphorus, nitrogen, fluorine and particulate suspended solids, SS) removal; Turbidity improvement; And there is provided a method for treating contaminated water, characterized in that the sludge volume is reduced.

In another aspect of the present invention, an inorganic metal compound may be additionally added to the polychlorinated aluminum silicate-based coagulant composition. As the inorganic metal compound, Si, Ca, Mg, La, Be, B, Fe, Ga, Ge, Y, Zr, Na, and K may be used, but are not limited thereto.

In one aspect of the present invention, _{the concentration of Al 2} O ₃ is 10 to 19% by weight, basicity is 50 to 75%, chloride (Cl) is 10 to 20% by weight, (SO ₄ ) ^2- is 0.1 to It is 5% by weight, and SiO ₂ is provided with a coagulant composition for water purification and one *? * wastewater treatment comprising aluminum silicate polychloride sulfate of 0.01 to 2% by weight.

In one aspect of the present invention, the aluminum silicate polychloride sulfate has _{a concentration of Al 2} O ₃ of 10% by weight or more and less than 19% by weight, a basicity of 50% or more and less than 70%, and chloride (Cl) of 10-20% by weight. %, and (SO ₄ ) ^2- is 0.5 to 4% by weight, and SiO ₂ may be more than 0.01% by weight and 2% by weight or less.

In one aspect of the present invention, the aluminum silicate polychloride sulfate has _{a concentration of Al 2} O ₃ of 10 to 18% by weight, a basicity of 55 to 68%, and a chloride (Cl) of 10 to 20% by weight, (SO ₄ ) ^2- is 0.7 to 4% by weight, and SiO ₂ may be 0.015 to 1.5% by weight.

In one aspect of the present invention, the aluminum silicate polychloride sulfate has _{a concentration of Al 2} O ₃ of 10 to 18% by weight, a basicity of 50 to 65%, and a chloride (Cl) of 10 to 20% by weight, (SO ₄ ) ^2- is 2 to 4.5% by weight, and SiO ₂ may be 0.5 to 1.5% by weight.

In one aspect of the present invention, the polychlorinated aluminum silicate-based flocculant is more specifically, 1) _{the concentration of Al 2} O ₃ is 10 to 19% by weight, 10 to 19% by weight, 10 to 18% by weight, 10 to 17% by weight, 10 to 16% by weight, 10 to 15.5% by weight, 10 to 15% by weight, 10 to 14% by weight, 10 to 13% by weight, may be 10 to 12% by weight; 2) Basicity 50-75%, 50-74%, 50-73%, 50-72%, 50-71%, 50-70%, 50-69%, 50-68%, 50-67%, 50 It can be ~66%, 50~65%, 50~64%, 50~63%, 50~62%, 50~61%, 50~60%, where the upper limit of each basicity is less than that value, or May be less than that number; 3) chloride (Cl) may be 10 to 20% by weight, 10 to 19% by weight, 10 to 18% by weight, 10 to 17% by weight, 10 to 16% by weight, 10 to 15% by weight; 4) (SO ₄ ) ^2- This is 0.1~5 wt%, 1~4.9 wt%, 1~4.8 wt%, 1~4.7 wt%, 1~4.6 wt%, 1~4.5 wt%, 1~4.4 wt% , 1 to 4.3% by weight, 1 to 4.2% by weight, 1 to 4.1% by weight, 1 to 4.0% by weight, 0.5 to 4.0% by weight, 0.7 to 4.0% by weight, and _{the lower limit of (SO 4} ) ^2- is 0.1% by weight %, 0.5%, 0.7%, 1%, 1.1%, 1.2%, 1.3%, 1.4% or 1.5% by weight; 5) SiO ₂ is 0.01 to 2% by weight, more than 0.01% by weight and 2% by weight or less, 0.015 to 2% by weight, 0.015 to 1.5% by weight, 0.1 to 2% by weight, 0.5 to 1.5% by weight, 1 to 1.5% by weight I can.

Unless otherwise stated in the specification,% means% by weight.

In the case of the polychlorinated aluminum silicate coagulant prepared by the method according to the present invention, the floc formation is larger and harder even when a small amount is added compared to commonly used polyaluminum chloride and aluminum sulfate, so that water treatment efficiency can be improved, and algae Water treatment efficiency is excellent even when inflow, and at the same time, it can significantly lower the dissolution as well as particulate SS and turbidity in wastewater containing dissolved phosphorus, nitrogen, fluorine, etc., and stable water treatment is possible as well as stability by reducing the volume of sludge. and the advantage of being significantly improved, SiO ₂ Mitcham visible there is shown a possible manufacturing process of the normal benefits of producing even 19% when making the high concentration of aluminum at least 18% oxidation products eoryeowoona SiO ₂ was added.

1 shows the experimental results of testing the stability of a product by concentration of aluminum oxide.
2 shows the experimental results of testing the stability of products by basicity.
Figure 3 shows the experimental results of testing the stability of the product by chloride concentration.
Figure 4 shows the experimental results of testing the stability of the product by sulfate ion concentration.
5A and 5B show experimental results for testing the stability of products by silicon dioxide concentration.
6 shows the experimental results of testing the stability of each coagulant product.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for describing the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples according to the gist of the present invention. .

Example

Manufacturing example. Preparation of flocculant

Step a : (Preparation of the first mixture) Aluminum oxide 40 to 70% by weight of aluminum hydroxide (Al(OH) ₃ ) 15 to 25% by weight and 20 to 40% hydrochloric acid 50 to 75% by weight, and 10 to 35% by weight of water % Is mixed to prepare aluminum chloride having 9 to 17% by weight of aluminum oxide and 0.1 to 25% of basicity.

Step b : (Preparation of secondary mixture) Aluminum oxide 40-70% by weight aluminum hydroxide (Al(OH) ₃ ) 8-15% by weight, 60-98% sulfuric acid 12-30% by weight, water 60-80% % Is mixed to prepare aluminum sulfate of 5 to 9% by weight of aluminum oxide and 10 to 30% of sulfate ions.

Step c _{: 10-30% by weight of NaOH with a concentration of 10-50% by weight of sodium oxide (Na 2} O) in 70-90% by weight of the secondary mixture (NaOH can be replaced with sodium aluminate, in this case, the secondary mixture 10 to 50% by weight of sodium aluminate is added to 50 to 90% by weight) and reacted at a temperature of 50 to 200°C to obtain a basic aluminum sulfate of 3 to 8% by weight of aluminum oxide and 10 to 27% of sulfate ions. To manufacture.

Step d : 60 to 85% by weight of the primary mixture and 15 to 40% by weight of the basic aluminum sulfate obtained above are mixed and reacted at a temperature of 100 to 200°C to obtain 8 to 14% by weight of aluminum oxide and 15 to 40% by weight of the basicity. To prepare aluminum chloride sulfate.

Step e : Then, sodium aluminate having a concentration of 10 to 40% by weight of sodium oxide (Na _{2 O) and 15 to 30% by weight of aluminum oxide (Al 2} O ₃ ) is added to 10 to 25% by weight of aluminum chloride sulfate. A mixture reaction of 0.1 to 10% by weight of sodium silicate, which is 10 to 40% by weight, and 7 to 40% by weight of water, at a temperature of 30 to 100°C at a rate of 5000 to 20000 rpm, to prepare aluminum polychloride sulfate aluminum silicate. At this time, sodium silicate can be replaced with sodium aluminum silicate or zeolite. In addition, sodium silicate may be administered not only in step e, but also in steps a, b, c or d.

Example.

A flocculant as shown in the following table was prepared by the method as described in the above Preparation Example. For example, the coagulant according to Example 2 was prepared according to the following procedure:

Example of the manufacturing process of the coagulant according to Example 2:

Step a : (Preparation of the first mixture) Aluminum oxide 65% by weight of aluminum hydroxide (Al(OH) ₃ ) 24.6% by weight, 35% hydrochloric acid 72.5% by weight, and water 29% by weight are mixed to 16% by weight of aluminum oxide, Aluminum chloride having a basicity of 20% was prepared.

Step b : (Preparation of a secondary mixture) Aluminum oxide 65% by weight of aluminum hydroxide (Al(OH) ₃ ) 12.9% by weight, 98% of sulfuric acid 27.1% by weight, water 60% by weight of aluminum oxide 8.4% by weight, Aluminum sulfate with 26% sulfate ion was prepared.

Step c : 28.5% by weight of NaOH (NaOH can be replaced by sodium aluminate) having a concentration of 38.75% by weight of _{sodium oxide (Na 2} O) in 64.3% by weight of the secondary mixture is added to a temperature of 50 to 200°C. By reacting at, a basic aluminum sulfate having 5.4% by weight of aluminum oxide and 16.7% of sulfate ions was prepared.

Step d : 80% by weight of the first mixture and 20% by weight of the basic aluminum sulfate obtained above were mixed and reacted at a temperature of 100 to 200°C to prepare aluminum chloride sulfate having 13.9% by weight of aluminum oxide and 20% of basicity.

Step e : After that, sodium aluminate having a concentration of 20% _{sodium oxide (Na 2 O) and 26% by weight aluminum oxide (Al 2} O ₃ ) in 64.9% by weight of aluminum chloride sulfate is added to 16.9% by weight and 29% by weight of sodium silicate. 1.7% by weight and 16.5% by weight of water were mixed and reacted at a temperature of 30 to 100° C. at a rate of 5000 to 20000 rpm to prepare aluminum polychloride sulfate aluminum silicate. At this time, sodium silicate can be replaced with sodium aluminum silicate or zeolite. In addition, sodium silicate may be administered not only in step e, but also in steps a, b, c or d.

No. Al ₂ O ₃ basicity chloride SO ₄ ^2- SiO ₂ Example 1 10.5 60 13 2 0.5 Example 2 13 60 13 2 0.5 Example 2-1 13 60 13 2 0.1 Example 3 14 60 13 2 0.5 Example 4 16 60 13 2 0.5 Example 5 18 60 13 2 0.5 Example 6 19 60 13 2 0.5 Example 7 16 50 13 2 0.5 Example 8 16 55 13 2 0.5 Example 9 16 65 13 2 0.5 Example 10 16 70 13 2 0.5 Example 11 16 75 13 2 0.5 Example 12 16 60 10 2 0.5 Example 13 16 60 12 2 0.5 Example 14 16 60 14 2 0.5 Example 15 16 60 16 2 0.5 Example 16 16 60 18 2 0.5 Example 17 16 60 20 2 0.5 Example 18 13 60 13 One 0.5 Example 19 13 60 13 3 0.5 Example 20 13 60 13 4 0.5 Example 21 13 60 13 5 0.5 Example 22 13 60 13 2 0.01 Example 23 13 60 13 2 0.1 Example 23-1 13 60 13 2 0.5 Example 23-2 13 60 13 2 One Example 24 13 60 13 2 1.3 Example 24-1 13 60 13 2 1.5 Example 25 13 60 13 2 2 Example 26 10.5 60 12 2.7 1.6 Example 27 10.5 65 11 4 2 Example 28 12.5 60 13 2 One Example 29 16 55 16 3 0.5 Example 30 11 60 11 4 1.5 Example 31 12.5 65 14 2 One Example 32 16.5 60 16 3 0.5 Example 33 16 60 13 2 One Example 34 12.5 63 15 4.5 One Example 35 10.5 57 12 3.5 1.5 Example 36 16.5 60 13 1.5 0.5 Example 37 10.5 60 15 2 2 Example 38 12.5 65 12 One 1.5 Example 39 19 60 13 2 0.1 Example 40 19 60 13 2 One Example 41 19 60 13 2 1.5 Example 42 19 60 13 2 2 Comparative Example 1 13 60 13 2 0 Comparative Example 2 10.5 60 12 2.7 0 Comparative Example 3 10.5 65 11 4 0 Comparative Example 4 12.5 60 13 2 0 Comparative Example 5 16 55 16 3 0 Comparative Example 6 11 60 11 4 0 Comparative Example 7 12.5 65 14 2 0 Comparative Example 8 16.5 60 16 3 0 Comparative Example 9 16 60 13 2 0 Comparative Example 10 12.5 63 15 4.5 0 Comparative Example 11 10.5 57 12 3.5 0 Comparative Example 12 16.5 60 13 1.5 0 Comparative Example 13 10.5 60 15 2 0 Comparative Example 14 12.5 65 12 One 0 Comparative Example 15 19 60 13 2 0 Comparative Example 16 13 60 13 0 0.5

Experimental example

Experimental Example 1. Comparison by properties of coagulant (Sewage treatment plant A)

The following is a comparative experiment of Jar-Test for each type of coagulant using raw water from a sewage treatment plant. As shown in the following table, Examples 1 to 6 were added to the sewage collected from area A at a concentration of 55 ppm, respectively, and suspended solids (SS), total phosphorus (Total-P, TP), and SV ₃₀ values Was measured. SS, TP, and SV ₃₀ were measured using the method described in (Water Pollutant Waste Soil Pollution) Process Test Method (Article Technology Editorial Department).

1) Comparison by aluminum oxide

- Coagulant composition Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Appearance Al ₂ O ₃ (% by weight) 10.5 13 14 16 18 19 basicity(%) 60 60 60 60 60 60 chloride(%) 13 13 13 13 13 13 Sulfate ion (%) 2 2 2 2 2 2 SiO ₂ (%) 0.5 0.5 0.5 0.5 0.5 0.5 Input amount (ppm) 55 55 55 55 55 55 SS (mg/L) 1.9 1.5 1.2 0.9 0.6 0.5 T-P (mg/L) 1.5 1.2 0.7 0.5 0.3 0.3 SV ₃₀ (ml/L) 890 810 570 540 500 490 Remark 1) Raw water phase: SS 7.6mg/L, TP 4.5mg/L, SV ₃₀ 970ml/L
2) For comparison according to the aluminum oxide properties of the coagulant according to the present invention, the conditions of basicity 60%, chloride 13%, sulfate ion 2%, and SiO ₂ 0.5% are the same, and the Al ₂ O ₃ concentration is different. . result 1) As shown above, the optimal Al ₂ O ₃ is judged to be 14% or more.
2) Stability was not secured to prepare more than 19 _{% of Al 2} O ₃ at 60% basicity.

2) Comparison by basicity

- Coagulant composition Example 7 Example 8 Example 4 Example 9 Example 10 Example 11 Appearance Al ₂ O ₃ (% by weight) 16 16 16 16 16 16 basicity(%) 50 55 60 65 70 75 chloride(%) 13 13 13 13 13 13 Sulfate ion (%) 2 2 2 2 2 2 SiO ₂ (%) 0.5 0.5 0.5 0.5 0.5 0.5 Input amount (ppm) 55 55 55 55 55 55 SS (mg/L) 1.5 0.9 0.8 0.6 0.4 0.4 T-P (mg/L) 1.0 0.6 0.5 0.4 0.3 0.3 SV ₃₀ (ml/L) 610 570 550 540 520 500 Remark 1) Raw water phase: SS 8.1mg/L, TP 4.3mg/L, SV ₃₀ 960ml/L
2) For comparison according to the properties of aluminum oxide of the coagulant according to the present invention, the conditions of Al ₂ O ₃ 16%, chloride 13%, sulfate ion 2%, SiO ₂ 0.5% were equally fixed, and basicity Manufactured at different concentrations. result 1) As shown in the above result, the optimal basicity is judged to be 50% or more.
2) Stability was not secured to prepare more than 75% of basicity.

3) Comparison by chloride

- Coagulant composition Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Appearance Al ₂ O ₃ (% by weight) 16 16 16 16 16 16 basicity(%) 60 60 60 60 60 60 chloride(%) 10 12 14 16 18 20 Sulfate ion (%) 2 2 2 2 2 2 SiO ₂ (%) 0.5 0.5 0.5 0.5 0.5 0.5 Input amount (ppm) 55 55 55 55 55 55 SS (mg/L) 1.0 0.9 0.9 0.8 0.7 0.6 T-P (mg/L) 1.2 0.6 0.5 0.5 0.4 0.3 SV ₃₀ (ml/L) 570 550 540 530 530 510 Remark 1) Raw water phase: SS 7.4mg/L, TP 3.9mg/L, SV ₃₀ 930ml/L
2) For comparison according to the properties of aluminum oxide of the coagulant according to the present invention, the conditions of Al ₂ O ₃ 16%, basicity 60%, sulfate ion 2%, SiO ₂ 0.5% were equally fixed, and chloride Manufactured at different concentrations. result 1) As shown above, the optimal chloride concentration was judged to be 12% or higher.
2) Stability was not secured to prepare more than 20% of chloride.

4) Comparison by sulfate ion

- Coagulant composition Comparative Example 16 Example 18 Example 2 Example 19 Example 20 Example 21 Appearance Al ₂ O ₃ (% by weight) 13 13 13 13 13 13 basicity(%) 60 60 60 60 60 60 chloride(%) 13 13 13 13 13 13 Sulfate ion (%) 0 One 2 3 4 5 SiO ₂ (%) 0.5 0.5 0.5 0.5 0.5 0.5 Input amount (ppm) 55 55 55 55 55 55 SS (mg/L) 2.1 1.7 1.5 1.4 1.4 1.3 T-P (mg/L) 1.5 1.2 1.1 1.1 1.0 1.0 SV ₃₀ (ml/L) 870 820 810 800 790 790 Remark 1) Raw water phase: SS 7.9mg/L, TP 4.1mg/L, SV ₃₀ 960ml/L
2) For comparison according to the aluminum oxide properties of the coagulant according to the present invention, Al ₂ O ₃ 13%, basicity 60%, chloride 13%, SiO ₂ 0.5% conditions were the same, and sulfate ion Manufactured at different concentrations. result 1) As shown in the above results, the optimal sulfate ion concentration is judged to be 1% or more.
2) Stability was not secured to prepare more than 5% of sulfate ions.

5) Comparison of _{SiO 2 stars}

- Coagulant composition Comparative Example 1 Example 22 Example 23 Example 2 Example 24 Example 25 Appearance Al ₂ O ₃ (% by weight) 13 13 13 13 13 13 basicity(%) 60 60 60 60 60 60 chloride(%) 13 13 13 13 13 13 Sulfate ion (%) 2 2 2 2 2 2 SiO ₂ (%) 0 0.01 0.1 0.5 1.3 2 Input amount (ppm) 55 55 55 55 55 55 SS (mg/L) 1.6 1.6 1.4 1.3 1.2 1.1 T-P (mg/L) 1.7 1.4 1.2 1.1 0.9 0.8 SV ₃₀ (ml/L) 810 810 800 790 790 780 Remark 1) Raw water phase: SS 8.2mg/L, TP 4.0mg/L, SV ₃₀ 970ml/L
2) For comparison according to the aluminum oxide properties of the coagulant according to the present invention, the conditions of Al ₂ O ₃ 13%, basicity 60%, chloride 13%, and sulfate ion 2% are the same, and the SiO ₂ concentration is different. . result 1) As shown above, the optimal sulfate ion concentration was judged to be 0.1% or higher.
2) Stability was not secured to prepare more than 2% of _{SiO 2.}

Experimental Example 2. Comparison by coagulant

1) Water purification plant

① Water purification plant A

- Example 26 Comparative Example 2 Company A Company B Appearance Al ₂ O ₃ (% by weight) 10.5 10.5 10.5 10.5 basicity(%) 60 60 70 60 chloride(%) 12 12 - - Sulfate ion (%) 2.7 2.7 - - SiO ₂ (%) 1.6 0 - - Input amount (ppm) 15 15 15 15 pH 7.70 7.71 7.70 7.68 Turbidity (NTU) 0.321 0.357 0.420 0.517 Al (ml/L) 0.043 0.055 0.095 0.107 Remark 1) Raw water phase: pH 7.91, turbidity 5.71 NTU, Al 0.025mg/l result 1) SiO ₂ in the case of the example 26 was added SiO ₂ Comparative Example 2 is not more turbidity removal efficiency is not added hayeoteum slightly superior.
2) As for the elution of aluminum, _{Example 26 to which SiO 2} was added was less eluted than Comparative Example 2.

② Water purification plant B

- Example 27 Example 28 Example 29 Comparative Example 3 Comparative Example 4 Comparative Example 5 Company B Appearance Al ₂ O ₃ (% by weight) 10.5 12.5 16 10.5 12.5 16 10.5 12.5 basicity(%) 65 60 55 65 60 55 60 60 chloride(%) 11 13 16 11 13 16 - - Sulfate ion (%) 4 2 3 4 2 3 - - SiO ₂ (%) 2 One 0.5 0 0 0 - - Input amount (ppm) 12 12 12 12 12 12 12 12 pH 7.64 7.62 7.59 7.65 7.63 7.59 7.58 7.55 Turbidity (NTU) 0.521 0.411 0.321 0.552 0.447 0.345 0.819 0.527 Al (ml/L) 0.035 0.043 0.050 0.043 0.049 0.061 0.101 0.114 Remark 1) Raw water phase: pH 7.91, turbidity 5.71 NTU, Al 0.025mg/l result 1) _{Example 27 to which SiO 2} was added had slightly excellent turbidity removal efficiency, and less aluminum was eluted.

2) Sewage treatment plant

① A sewage treatment plant

- Example 30 Example 31 Example 32 Comparative Example 6 Comparative Example 7 Comparative Example 8 Appearance Al ₂ O ₃ (% by weight) 11 12.5 16.5 11 12.5 16.5 basicity(%) 60 65 60 60 65 60 chloride(%) 11 14 16 11 14 16 Sulfate ion (%) 4 2 3 4 2 3 SiO ₂ (%) 1.5 One 0.5 0 0 0 Input amount (ppm) 55 55 55 55 55 55 SS (mg/L) 1.5 0.8 0.4 1.8 1.0 0.6 T-P (mg/L) 1.2 0.8 0.3 1.4 0.9 0.5 SV ₃₀ (ml/L) 790 690 500 810 700 530 Remark 1) Raw water phase: SS 7.5mg/L, TP 4.1mg/L, SV ₃₀ 950ml/L result 1) Example 30-32 SiO ₂ was added, the water treatment efficiency hayeoteum superior to Comparative Examples 6 ~ 8 SiO ₂ is not added.

② B sewage treatment plant

- enemy Example 33 Comparative Example 9 Polyaluminum chloride Appearance Al ₂ O ₃ (% by weight) - 16 16 17 basicity(%) - 60 60 40 chloride(%) - 13 13 21 Sulfate ion (%) - 2 2 0.3 SiO ₂ (%) - One 0 - Input amount (ppm) - 40 40 4 Day 1 SS (mg/L) 15.2 3.7 4.1 5.6 T-P (mg/L) 3.45 0.54 0.67 1.12 SV ₃₀ (ml/L) 940 520 550 620 Interface (cm) - 250 290 350 Day 2 SS (mg/L) 14.8 3.4 3.6 5.1 T-P (mg/L) 3.71 0.57 0.69 1.14 SV ₃₀ (ml/L) 930 560 610 650 Interface (cm) - 300 320 370 Day 3 SS (mg/L) 16.4 3.9 4.3 5.8 T-P (mg/L) 3.87 0.61 0.68 1.08 SV ₃₀ (ml/L) 900 500 540 600 Interface (cm) - 260 290 340 Day 4 SS (mg/L) 15.5 3.5 3.6 5.4 T-P (mg/L) 2.92 0.49 0.65 1.07 SV ₃₀ (ml/L) 920 570 580 630 Interface (cm) - 240 270 360 Remark 1) The height of the sedimentation basin interface of the B sewage treatment plant is 600cm. result 1) _{Example 33 to which SiO 2} was added has excellent water treatment efficiency.

3) Wastewater treatment plant

① Fluorine wastewater

- Example 34 Comparative Example 10 Company A Company B Company C Appearance Al ₂ O ₃ (% by weight) 12.5 12.5 12.5 12.5 12.5 basicity(%) 63 63 70 60 60 chloride(%) 15 15 - - - Sulfate ion (%) 4.5 4.5 - - - SiO ₂ (%) One 0 - - - Input amount (ppm) 1,500 1,500 1,500 1,500 1,500 SS (mg/l) 1.0 1.2 1.5 2.2 2.3 F (mg/l) 218 224 378 351 361 Remark 1) Raw water phase: SS 17.4mg/l, F 1,675mg/l result 1) The water treatment efficiency of Example 34 to which _{SiO 2 was added was excellent.}

② Paper wastewater

- Example 35 Comparative Example 11 Company A Company B Company C Appearance Al ₂ O ₃ (% by weight) 10.5 10.5 10.5 10.5 10.5 basicity(%) 57 57 70 60 60 chloride(%) 12 12 - - - Sulfate ion (%) 3.5 3.5 - - - SiO ₂ (%) 1.5 0 - - - Input amount (ppm) 1,500 1,500 1,500 1,500 1,500 Polymer input (ppm) 2.7 2.7 2.7 2.7 2.7 SS (mg/l) 226 248 294 300 304 COD (mg/l) 326 330 368 356 350 Remark 1) Raw water phase: SS 524mg/l, COD 620mg/l result 1) The water treatment efficiency of Example 35 to which _{SiO 2 was added was excellent.}

③ Automobile wastewater

- Example 36 Comparative Example 12 Polyaluminum chloride Low-basic polyaluminum chloride Appearance Al ₂ O ₃ (% by weight) 16.5 16.5 17 15 basicity(%) 60 60 40 15 chloride(%) 13 13 21 26 Sulfate ion (%) 1.5 1.5 0.3 0.3 SiO ₂ (%) 0.5 0 - - Input amount (ppm) 400 400 400 400 25% NaOH input (ppm) 350 350 350 350 Polymer input (ppm) 3 3 3 3 SS (mg/l) 3 4 7 10 T-P (mg/l) 0.25 0.38 1.2 1.0 T-N (mg/l) 1.2 1.4 2.3 2.4 Remark 1) Raw water phase: SS 750mg/l, T-P 16.8mg/l, T-N 70mg/l result 1) The water treatment efficiency of Example 36 to which _{SiO 2 was added was excellent.}

4) algae removal

① Anabnena

- Example 37 Comparative Example 13 Polychloride
aluminum Company B Company C Appearance Al ₂ O ₃ (% by weight) 10.5 10.5 10.5 10.5 10.5 basicity(%) 60 60 40 60 60 chloride(%) 15 15 13 - - Sulfate ion (%) 2 2 0.3 - - SiO ₂ (%) 2 0 - - - Input amount (ppm) 15 15 15 15 15 pH 7.59 7.59 7.48 7.58 7.57 Turbidity (NTU) 0.187 0.202 0.671 0.448 0.466 KMnO ₄ (mg/l) 2.15 2.41 2.84 2.53 2.50 Remark 1) Raw water phase: pH 7.71, turbidity 7.21 NTUl, KMnO ₄ 5.32mg/l
2) Compare the water treatment efficiency after adding algae Anabnena to the raw water of the water purification plant. result 1) The water treatment efficiency of Example 37 to which _{SiO 2 was added was excellent.}

② Miwcystis

- Example 38 Comparative Example 14 Polychloride
aluminum Company B Company C Appearance Al ₂ O ₃ (% by weight) 12.5 12.5 17 12.5 12.5 basicity(%) 65 65 40 60 60 chloride(%) 12 12 21 - - Sulfate ion (%) One One 0.3 - - SiO ₂ (%) 1.5 0 - - - Input amount (ppm) 20 20 20 20 20 pH 7.46 7.45 7.32 7.43 7.42 Turbidity (NTU) 0.211 0.226 0.695 0.445 0.451 KMnO ₄ (mg/l) 3.14 3.52 3.95 3.71 3.72 Remark 1) Raw water phase: pH 7.65, turbidity 11.2NTU, KMnO ₄ 6.71mg/l
2) Compare the water treatment efficiency after adding algae Miwcysitis to the raw water of the water purification plant. result 1) The water treatment efficiency of Example 38 to which _{SiO 2 was added was excellent.}

As seen through the above experimental examples, the coagulant composition according to the present invention measures factors such as _{SS, TP, SV 30} , TN, turbidity, Al elution, interface height, F removal efficiency, COD value, and KMnO _{4 value.} As a result, it can be seen that it shows a very good effect.

As described above, specific parts of the present invention have been described in detail, and it is obvious that these specific techniques are only preferred embodiments, and the scope of the present invention is not limited thereto for those of ordinary skill in the art. Therefore, it will be said that the practical scope of the present invention is defined by the appended claims and their equivalents.

Claims (2)

(a) Aluminum oxide 40 to 70% by weight of aluminum hydroxide (Al(OH) ₃ ) 15 to 25% by weight of 20 to 40% hydrochloric acid 50 to 75% by weight, and 10 to 35% by weight of water are mixed to produce aluminum oxide 9 -17% by weight, preparing an aluminum chloride having a basicity of 0.1 to 25%;
(b) Aluminum oxide 40 to 70% by weight of aluminum hydroxide (Al(OH) ₃ ) 8 to 15% by weight, 60 to 98% by weight of sulfuric acid 12 to 30% by weight, and 60 to 80% by weight of water are mixed to form aluminum oxide 5 to 9% by weight, preparing aluminum sulfate with 10 to 30% of sulfate ions;
(c) 10-30% by weight of NaOH having a concentration of 10-50% by weight of _{sodium oxide (Na 2} O) is added to 70-90% by weight of the mixture obtained in step (b), or the mixture obtained in (b) Adding 10 to 50% by weight of sodium aluminate to 50 to 90% by weight and reacting at a temperature of 50 to 200°C to prepare a basic aluminum sulfate having 3 to 8% by weight of aluminum oxide and 10 to 27% by weight of sulfate ions;
(d) 60 to 85% by weight of the mixture obtained in step (a) and 15 to 40% by weight of the basic aluminum sulfate obtained in step (c) are mixed and reacted at a temperature of 100 to 200°C to 8 to 14 weight of aluminum oxide %, preparing an aluminum chloride sulfate having a basicity of 15 to 40%; And
(e) 10 to 25% by weight of sodium aluminate _{with a sodium oxide (Na 2} O) concentration of 10 to 40% by weight, aluminum oxide (Al ₂ O ₃ ) concentration of 15 to 30% by weight in 35 to 80% by weight of aluminum chloride sulfate, 10 to 40% by weight sodium silicate or 10 to 40% by weight sodium aluminum silicate or 10 to 70% by weight zeolite 0.1 to 10% by weight and 7 to 40% by weight of water 5,000 to 20,000 rpm at a temperature of 30 to 100 °C It is prepared including the step of mixing reaction at a rate of,
It is represented by the following formula (1),
Al ₂ O ₃ concentration is 10 to 19% by weight, basicity is 50% or more and less than 70%, chloride (Cl) is 12% by weight or more and less than 20% by weight, (SO ₄ ) ^2- is 0.1% or more by weight Less than 5% by weight, SiO ₂ containing 0.1% by weight or more and less than 2% by weight of polysilicon sulphate polysulphate, a coagulant composition for water purification and sewage and wastewater treatment.
[Formula 1]
Al _a (OH) _b Cl _c (SO ₄ ) _d (SiO ₂ )
In the above formula,
a=6, 9≤b≤13, 3≤c≤7, d≤1, or
a=7, 10≤b≤15, 4≤c≤9 d≤1.
Including the step of treating the coagulant composition according to claim 1 in contaminated water,
As the above treatment,
Removal of dissolved phosphorus, nitrogen, fluorine and suspended solids (SS); Turbidity improvement; And characterized in that it exhibits a reduction in the volume of sludge,
Contaminated water treatment method.

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