KR20060120770A - Manufacturing method of poly aluminium chloric silicate salt solution using wasted aluminium chloride solution - Google Patents

Abstract

A preparation method of a poly aluminium chloric silicate salt solution with low production cost and excellent storage characteristics by using a waste aluminium chloride solution, and a preparation method of a poly aluminium chloric silicate salt solution that can be used as a water treatment agent and a sizing agent for papermaking, and particularly has high coagulation effect and fast sedimentation rate when used as the water treatment agent are provided. A preparation method of poly aluminium chloric silicate salt solution using waste aluminium chloride solution comprises: a first process of preparing a waste aluminum chloride solution; a second process of preparing a zeolite or zeolite powder in the moisture-contained state using aluminum dross; and a third process of putting the zeolite prepared in the second process into the waste aluminum chloride solution prepared in the first process to mix the zeolite with the waste aluminum chloride solution. The zeolite of the second process is prepared by performing a zeolite preparation method comprising: a first process of mixing aluminum dross with water to prepare an aluminum dross mixed solution; a second process of mixing a sodium silicate solution with a sodium hydroxide solution to prepare an alkaline salt solution; a third process of dissolving the alkaline salt solution into the aluminum dross mixed solution; a fourth process of filtering a dissolved solution of the third process; and a fifth process of mixing a sodium silicate solution with a filtrate of the fourth process, agitating the mixture, filtering the agitated material, storing a filtrate separately, and collecting a filtered material to prepare moisture-containing zeolite or prepare zeolite powder by naturally drying the moisture-containing zeolite.

Description

MANUFACTURING METHOD OF POLY ALUMINIUM CHLORIC SILICATE SALT SOLUTION USING WASTED ALUMINIUM CHLORIDE SOLUTION}

1 is a manufacturing process chart of the polyaluminum chloride silicate solution of the present invention

The present invention relates to a method for producing a polyaluminum chloride silicate solution using a waste aluminum chloride solution.

The waste aluminum chloride solution is usually discharged as waste in aluminum condenser manufacturing process or pigment manufacturing process, and is recycled as a flocculant for water treatment, or may be separated into waste hydrochloric acid and recycled as a neutralizing agent.

However, if the waste aluminum chloride solution is used as a flocculant for water treatment, the amount of neutralizing agents such as caustic soda increases, and the neutralization treatment, sulfide treatment, precipitation method and adsorption and ions are performed to remove impurities contained in the waste aluminum chloride solution. There was a problem to be used after treatment by the exchange law.

Research has been done to recycle waste aluminum chloride solution.

In Korean Patent Publication No. 10-0380926 (Method for preparing a polymer aluminum coagulant using waste aluminum chloride solution), waste aluminum pieces are introduced into a waste aluminum chloride solution containing copper to deposit and remove copper, and the copper A method for producing a polymer aluminum flocculant by adding a base to the waste aluminum chloride solution from which is removed is produced to produce a polymer aluminum complex.

However, the above invention is to remove the copper by using the waste aluminum chloride solution discharged to the waste water in the copper-phthalocyanine pigment manufacturing process, and to prepare a polymer aluminum complex by adding caustic soda as a base, a flocculant for water treatment When used as a low content of the inorganic basic coagulant has a problem that the coagulation effect is lowered and the precipitation rate is lowered the effect.

Therefore, there is a need for further research on a method for recycling waste aluminum chloride.

Meanwhile, Poly Aluminum Chloric Silicate Salt (Al _a (OH) _b (Cl) _c (Si) _d ) is a high concentration of the existing polyaluminum chloride (PAC) flocculant, aluminum oxide (Al ₂ O ₃ ) The concentration was increased to 17%, and the addition of silicic acid (silicate) to improve the cohesive performance is called PACS. Appearance is transparent, the product of Al ₂ O ₃ concentration of 16 to 18%, basicity of 45 to 50% is generally used, mainly used as a flocculant for water treatment.

In Korean Patent Application Publication No. 10-0480454 (method for producing a basic aluminum silicate) filed by the applicant of the present invention, the aluminum material is dissolved to form a precipitate with sodium silicate, which is dissolved with sulfuric acid or hydrochloric acid, and then polysilicate or polysulfate silicate. Disclosed is a method for producing the same.

However, the present invention has a problem in that the production cost is high because expensive hydrochloric acid should be used.

Therefore, there is a need for a method for producing a polyaluminum silicate having excellent efficiency at a low cost along with a method for recycling the waste aluminum chloride solution.

In order to solve the above problems, an object of the present invention is to provide a method for producing a polyaluminum chloride silicate solution having low production cost and excellent shelf life using a waste aluminum chloride solution.

In addition, the present invention provides a polyaluminum chloride silicate solution that can be used as a water treatment agent, a paper-making size agent, and the like, in particular, when used as a water treatment agent to provide a polyaluminum chloride silicate solution having a large coagulation effect and a fast settling effect. There is this.

The present invention relates to a method for producing a polyaluminum chloride silicate solution using waste aluminum chloride.

A method for producing a polyaluminum chloride silicate (PACS) solution using waste aluminum chloride of the present invention is a first step of preparing a waste aluminum chloride solution, a second step of producing a zeolite in a moisture state using an aluminum material (Aluminum dross) In the waste aluminum chloride solution prepared in the step 1 and the first step, 1 to 5% by weight of the zeolite in the moisture state prepared in the second step is added, or 6 to 10% by weight of the zeolite in the moisture state is added to the waste aluminum solution. In the third step of preparing a polyaluminum chloride silicate solution by mixing 20 to 70% by weight of water in the mixed solution.

In addition, the method for producing a polyaluminum chloride silicate (PACS) solution using the waste aluminum chloride of the present invention, the first step of preparing a waste aluminum chloride solution, using the aluminum material (aluminum dross) to produce a zeolite in a moisture state To the waste aluminum chloride solution prepared in the second step and the first step, add 0.3 to 2% by weight of the zeolite powder prepared in the second step, or add 3 to 10% by weight of the zeolite powder to the waste aluminum solution. 40 to 100% by weight of the mixed solution is mixed with the third step of producing a polyaluminum chloride silicate solution.

On the other hand, the method of manufacturing the zeolite of the second step, the first step to prepare a mixture of aluminum material by adding water to the aluminum material (aluminum dross) 3 to 6 times the weight of the aluminum material, sodium silicate in a caustic soda solution The second step of preparing an alkali salt solution by adding and mixing 1 to 5% by volume of the caustic soda solution with the volume of the caustic soda solution, and adding the alkali salt solution prepared in the second step to the aluminum remixed solution of the first step The aluminum material of the first step is added to the filtrate of the third step, the fourth step of filtering the dissolved solution of the third step, the fourth step of dissolving the solution of the third step, and the fourth step of melting The mixture is stirred at a rate of 70 to 100 ml per 100 g, mixed, and stirred. The agitated solution is filtered to store the filtrate separately, and the filtrate is collected to prepare a zeolite in a humid state, or the zeolite in a humid state is naturally dried. Zeolite It consists of a fifth process of making powder.

The filtrate stored separately during the filtration of the fifth process is recycled to prepare an aluminum mixture by mixing the mixture into aluminum instead of water to prepare the aluminum mixture of the first process.

In the waste aluminum chloride solution (wasted AlCl ₃ solution) used in the present invention, Al ₂ O ₃ generated in the aluminum condenser manufacturing process was used at a waste aluminum chloride solution having a pH of 5.8 to 6.0% and a pH of 0.5 or less.

The waste aluminum chloride solution may be used as a water treatment agent of wastewater directly, in which case there is a problem in that a large amount of neutralizing agent is used.

When the polyaluminum chloride silicate (PACS) solution is prepared from the waste aluminum chloride solution, the manufacturing cost is significantly lower than that of the polyaluminum chloride silicate solution using the aluminum chloride solution. In addition, since the zeolite used in the production of the polyaluminum chloride silicate solution is manufactured using an aluminum material, it is possible to prepare a polyaluminum chloride silicate solution which is much lower in cost than the general polyaluminum silicate solution and has an excellent effect. have.

Poly Aluminum Chloric Silicate Salt (Al _a (OH) _b (Cl) _c (Si) _d ) is a high concentration of the existing polyaluminum chloride (PAC) flocculant, the concentration of aluminum oxide (Al ₂ O ₃ ) It is called PACS to improve the cohesive performance by increasing the concentration to 17% and adding silicate. Appearance is transparent, the product of Al ₂ O ₃ concentration of 16 to 18%, basicity of 45 to 50% is generally used, mainly used as a flocculant for water treatment.

In the present invention, the zeolite used in the production of polyaluminum silicate is manufactured by using an aluminum material, and this aluminum material (Aluminum dross) refers to a slug generated when producing an aluminum ingot, and the aluminum metal component is 20 to 40% is contained and can be dissolved in caustic soda and used as raw material for water treatment agent or detergent.

The main components of aluminum material are aluminum oxide (Al ₂ O ₃ ; 30 to 50%) and metal aluminum (20 to 40%), except for small amounts of Si, Fe, Ca, K, Na, etc. It is contained.

Caustic soda (NaOH) used in the manufacture of zeolite is a strong alkaline material produced by causticization of sodium carbonate and electrolysis of sodium chloride. It is a general-purpose product used in almost all commodities such as soap, fiber, pulp, and water treatment as well as organic and inorganic materials. It is a chemical.

In the present invention, caustic soda is used as an aqueous solution, and its concentration is used in consideration of economical efficiency at 10 to 50%.

In addition, sodium silicate as the raw material to make the zeolite, and other silica derivatives (Sodium silicates), and the most widely used of the water-soluble silicate, and the molecular formula _{Na 2 O-nSiO 2 -xH 2} O as the inorganic compound, soil stabilization, adhesive, It is a material used for various purposes such as cement, pulp and paper, synthetic detergents and soaps, casting industry and water treatment.

In the present invention, sodium silicate was used in the liquid phase, and all of the Korean Industrial Standards 1-4 types sold on the market can be used, and among them, three kinds (specific gravity (20 ℃) 1.380 or more, water insoluble content 0.2% or less) Sodium oxide 9-9%, silicon dioxide 28-30%, iron (III) oxide 0.03%) are mainly used.

The inventors of the present invention have found that, when a polyaluminum silicate solution is prepared by mixing a zeolite prepared from an aluminum material using waste aluminum chloride solution while undergoing numerous trial and error, the economy and its effect are further increased.

However, it was found that when the zeolite in a humid state is mixed with the waste aluminum chloride solution by more than 5% by weight relative to the weight of the waste aluminum chloride solution, the polyaluminum chloride silicate solution gels gradually over time. In addition, it was found that the effect is extremely poor when mixed at less than 1% by weight.

Therefore, in the case of using the moisture-containing zeolite, it was found that adding 1 to 5% by weight of the zeolite to the waste aluminum chloride solution did not proceed with gelation, resulting in large shelf life and the greatest effect.

In addition, when the amount of zeolite added exceeds 5%, the gelation does not proceed when diluting with water. If the amount of zeolite added exceeds 10% by weight, the dilution ratio should be increased to prevent gelation. When the concentration is lowered, there is a problem that the efficiency is lowered, and even if the amount of water exceeds 70% by weight of the mixed solution of the waste aluminum chloride solution and zeolite, the concentration of the polyaluminum chloride silicate solution is low, the efficiency is lowered.

Therefore, after mixing 6 to 10% by weight of zeolite in a humid state with waste aluminum chloride solution, and then diluting water by adding 20 to 70% by weight relative to the weight of this mixture, the gelation does not proceed and the effect is high. It was found that an aluminum chloride silicate solution could be prepared.

On the other hand, instead of using a zeolite in a moist state, it is possible to use a zeolite powder made of powder by naturally drying the zeolite in a moisture state.

In this case, the addition of zeolite powder to the waste aluminum chloride solution in an amount of 0.3 to 2% by weight relative to the weight of the waste aluminum chloride solution does not proceed with gelation, thus the shelf life is large and its effect is great. I knew it was going.

In addition, when the amount of zeolite powder added is more than 2% by weight, water may be added and diluted to prevent gelation. When the amount of zeolite powder is more than 10% by weight, the amount of water to be added must be increased to increase the dilution ratio. There is a problem that the efficiency of the polyaluminum silicate solution is lowered and the efficiency is lowered, and even when the addition amount of water exceeds 100% by weight, the concentration of the polyaluminum chloride silicate solution is lowered and the efficiency is lowered.

Therefore, after mixing 3-10 wt% of zeolite powder in the waste aluminum chloride solution and adding 40-100 wt% of water to the weight of the mixed solution to prepare a polyaluminum chloride silicate solution, the gelation does not proceed. In addition, it was found that a polyaluminum silicate solution with high efficiency and high effect can be prepared.

On the other hand, the zeolite used in the present invention is manufactured by using an aluminum material (Aluminum dross), 80 to 120 of the alkaline salt solution per 100 g of aluminum material in a mixture of water in a weight ratio of 3 to 6 times the aluminum material mixed It has been found that adding and dissolving g is an excellent ratio of dissolving aluminum, increasing economics and effectiveness, and not allowing crystals to precipitate over time.

At this time, the alkali salt solution is prepared by mixing the aluminum material with caustic soda and sodium silicate at a volume ratio of 100: 1 to 5, and the amount of dissolution of aluminum is increased compared to the case of using only caustic soda, and it boils when dissolved. There is no overflow phenomenon, and the crystal is not precipitated, so the effect is excellent.

The alkali salt solution was added to the mixed solution of aluminum material, and the dissolved solution was filtered. Then, sodium silicate solution was added and filtered to prepare zeolite. At this time, the sodium silicate solution was in a ratio of 70 to 100 ml per 100 g of aluminum material. Putting and mixing the zeolite has the greatest effect, and the mixed solution is filtered to collect the filtrate to prepare a zeolite in a moist state. At this time, the filtrate can be stored separately and reused in place of water during zeolite production.

The zeolite in the moisture state is naturally dried and used as a zeolite powder.

When the zeolite of the present invention thus prepared is added to the waste aluminum chloride to prepare a polyaluminum chloride solution, when used as a water treatment agent, the effect of coagulation is greater than that of the conventional polyaluminum silicate solution, and the sedimentation rate is greater.

In addition, the polyaluminum silicate solution of the present invention can be used in a papermaking size agent or the like by a conventional method besides a water treatment agent.

Hereinafter, a method for preparing a polyaluminum chloride silicate solution using the waste aluminum chloride solution of the present invention will be described in detail.

<Manufacturing process of polyaluminum chloride silicate solution using waste aluminum chloride solution>

1. First Process: Material Preparation

Prepare a waste aluminum chloride solution (wasted AlCl ₃ solution) generated in the aluminum capacitor manufacturing process in the aluminum capacitor factory.

2. Second process: zeolite production

1) First Step: Preparation of Aluminum Material Mixture

Water is added to an aluminum dross and mixed 3 to 6 times the weight of aluminum to prepare an aluminum mixed solution.

2) second process: preparing alkaline salt solution

An alkali salt solution is prepared by adding 1-5 vol% of sodium silicate solution to the caustic soda solution, and adding 1-5 vol% of the caustic soda solution.

3) Process 3: Melting

The alkali salt solution prepared in the second process is added to the aluminum mixed solution of the first process at a rate of 80 to 120 g per 100 g of the aluminum material of the first process, and dissolved.

4) 4th process: Filtration

The lysate of the third step is filtered to discard the residue and the filtrate is separated.

5th process: zeolite production

The sodium silicate solution was added to the filtrate of the fourth step at a rate of 70-100 ml per 100 g of the aluminum material of the first step, followed by mixing and stirring.

This filtrate is filtered to store the filtrate separately, and the filtrate is collected to prepare a zeolite in a moist state.

In addition, the zeolite in a wet state may be naturally dried to prepare a zeolite powder.

At this time, the filtrate stored separately during the filtration of the mixed solution may be used in place of water when the mixed solution of the aluminum material of the first process.

3. Third process: preparation of polyaluminum chloride silicate solution

To the waste aluminum chloride solution prepared in the first step, add 1 to 5% by weight of the zeolite in the moisture state prepared in the second step, or add 6 to 10% by weight of the zeolite in the moist state to the waste aluminum solution. 20 to 70% by weight of the mixed solution was mixed to prepare a polyaluminum chloride silicate solution.

On the other hand, when using a zeolite powder, 0.3 to 2% by weight of the zeolite powder prepared in the second step to the waste aluminum chloride solution prepared in the first step, or 3 to 10% by weight of the zeolite powder to the waste aluminum solution mixed In one solution, water is added to 40 to 100% by weight of the mixed solution and mixed to prepare a polyaluminum chloride silicate solution.

The polyaluminum silicate solution (PACS) of the present invention prepared by the above process has a concentration of Al ₂ O ₃ of 5.0 to 11.0% and a pH of 1.5 to 2.5. In addition, the gelling does not occur, so it is excellent in shelf life and can be used for water treatment agents, paper size agents and the like.

Among them, when the polyaluminum silicate solution of the present invention is used as a water treatment agent, the flocculation effect is excellent, and the sedimentation speed is high, and the effect is excellent. Depending on the degree of contamination of the wastewater or wastewater, the dosage should be used differently.

Hereinafter, the production method of the polyaluminum silicate solution of the present invention will be described in detail through Examples and Experimental Examples, but these are not intended to limit the scope of the present invention.

Example 1 Preparation of Polyaluminum Chloride Silicate Solution Using Waste Aluminum Chloride Solution

An aluminum mixed solution was prepared by adding 300 g of water to 100 g of aluminum dross.

A caustic soda solution with a concentration of 33% was purchased and prepared in the market. Sodium silicate solution was prepared by purchasing Korean Industrial Standard No. 3.

To 100 mL of the prepared caustic soda solution, 1 mL of sodium silicate solution was added and mixed to prepare an alkali salt solution.

80 g of the alkali salt solution was added and dissolved in 400 g of the aluminum material mixture prepared above, and the filtrate was discarded and the filtrate was separated and prepared.

70 ml of sodium silicate solution was added to the filtrate, and the mixed solution was filtered. The filtrate was stored separately. The filtrate was collected to prepare a zeolite (moisture content 61.8%) in a humid state.

Meanwhile, a waste aluminum chloride solution (wasted AlCl ₃ solution; Al ₂ O ₃ 5.8%, pH 0.4) was prepared and purchased from JCC Korea.

The polyaluminum chloride silicate solution of the present invention was prepared by adding 50 g of the zeolite in the moisture state prepared above to 1,000 g of the prepared aluminum chloride solution.

The polyaluminum silicate solution is Al ₂ O ₃ 7.0%, the pH is characterized by 1.5.

<Example 2> Preparation of polyaluminum chloride silicate solution using waste aluminum chloride solution 2

400 g of water was added to 100 g of aluminum dross to prepare an aluminum mixture.

A caustic soda solution with a concentration of 50% was purchased and prepared on the market. Sodium silicate solution was prepared by purchasing Korean Industrial Standard No. 3.

To 100 mL of the prepared caustic soda solution, 2 mL of sodium silicate solution was added and mixed to prepare an alkali salt solution.

Into the 500 g of the aluminum material mixture prepared above, 90 g of the alkali salt solution was added and dissolved, and the filtrate was discarded and the filtrate was separated to prepare a filtrate.

80 ml of sodium silicate solution was added to the filtrate, and the mixed solution was filtered. The filtrate was stored separately. The filtrate was collected to prepare a zeolite (moisture content 62.1%) in a humid state.

Meanwhile, a waste aluminum chloride solution (wasted AlCl ₃ solution; Al ₂ O ₃ 6.0%, pH 0.4) was purchased from JCC Korea and prepared.

100 g of the zeolite in the moisture state prepared above was mixed with 1,000 g of the prepared aluminum chloride solution, and 550 g of water was added thereto to prepare a polyaluminum silicate solution of the present invention.

The polyaluminum silicate solution is Al ₂ O ₃ 7.5%, and has a pH of 1.7.

<Example 3> Preparation of polyaluminum chloride silicate solution using waste aluminum chloride solution 3

500 g of water was added to 100 g of aluminum dross to prepare an aluminum mixture.

A caustic soda solution with a concentration of 33% was purchased and prepared in the market. Sodium silicate solution was prepared by purchasing Korean Industrial Standard No. 3.

To 120 mL of the prepared caustic soda solution, 6 mL of sodium silicate solution was added and mixed to prepare an alkali salt solution.

100 g of the alkali salt solution was added and dissolved in 600 g of the aluminum material mixture prepared above, and the filtrate was discarded and the filtrate was separated and prepared.

90 ml of sodium silicate solution was added to the filtrate, and the mixed solution was filtered. The filtrate was stored separately. The filtrate was collected to prepare a zeolite in a humid state, and then dried naturally to prepare a zeolite powder.

On the other hand, a waste aluminum chloride solution (wasted AlCl ₃ solution; Al ₂ O ₃ 5.9%, pH 0.3) was prepared by purchasing from JCC Korea.

The polyaluminum silicate solution of the present invention was prepared by adding 20 g of the zeolite powder prepared above to 1,000 g of the prepared aluminum chloride solution.

The polyaluminum silicate solution is Al ₂ O ₃ 9.5%, pH is characterized by 1.8.

Example 4 Preparation of Polyaluminum Chloride Silicate Solution Using Waste Aluminum Chloride Solution 4

600 g of water was added to 100 g of aluminum dross to prepare an aluminum mixture.

A caustic soda solution with a concentration of 50% was purchased and prepared on the market. Sodium silicate solution was prepared by purchasing Korean Industrial Standard No. 3.

To 120 mL of the prepared caustic soda solution, 6 mL of sodium silicate solution was added and mixed to prepare an alkali salt solution.

120 g of the alkali salt solution was dissolved in 700 g of the aluminum material mixture prepared above, dissolved, filtered, discarded, and then separated from the filtrate.

90 ml of sodium silicate solution was added to the filtrate, and the mixture was filtered. The filtrate was stored separately. The filtrate was collected to prepare a zeolite in a humid state, and then dried naturally to prepare a zeolite powder.

Meanwhile, a waste aluminum chloride solution (wasted AlCl ₃ solution; Al ₂ O ₃ 6.0%, pH 0.3) was prepared by purchasing from JCC Korea.

100 g of the zeolite powder prepared above was added to 1,000 g of the prepared aluminum chloride solution, and then 880 g of water was added to the mixture to prepare a polyaluminum silicate solution of the present invention.

The polyaluminum silicate solution is Al ₂ O ₃ 10.6%, pH is characterized by 2.0.

Experimental Example 1 Comparative Experiment of Polyaluminum Chloride Solution According to Zeolite Addition in Moisture Condition

A waste aluminum chloride solution (wasted AlCl ₃ solution; Al ₂ O ₃ 6.0%, pH 0.3) was prepared by purchasing from JCC Korea.

Zeolite was prepared and prepared in the same manner as in Example 1.

5 g, 10 g, 30 g, 50 g, 60 g, 100 g and 200 g of zeolite prepared in 1,000 g of waste aluminum chloride solution were added to prepare polyaluminum silicate solution, respectively.

The results are shown in Table 1 below.

<Table 1> Comparative Results of PACS According to Zeolite Addition

Waste Aluminum Chloride Zeolite addition amount Remarks 1,000 g 5 g (0.5%) Not gelated 1,000 g 10 g (1%) Not gelated 1,000 g 30 g (3%) Not gelated 1,000 g 50 g (5%) Not gelated 1,000 g 60 g (6%) Gelled after 30 days 1,000 g 100 g (10%) Gelled after 1 day 1,000 g 200 g (20%) Gelled after 1 hour

As shown in the results of Table 1, gelation does not occur until 50 g is added, but when 60 g, 100 g, and 200 g exceeding 50 g are added, the polyaluminum chloride solution progresses with time. I could see.

When 5 g of zeolite was added, gelation did not proceed, but the effect of polyaluminum chloride was inferior. Therefore, when adding zeolite to waste aluminum chloride, adding 1 to 5% by weight of zeolite to the weight of waste aluminum chloride was recommended. As gelation does not proceed, the shelf life is large and the effect is great.

Experimental Example 2 Comparative Experiment of Polyaluminum Chloride Solution According to Zeolite and Water Addition in Moisture Condition

A waste aluminum chloride solution (wasted AlCl ₃ solution; Al ₂ O ₃ 5.8%, pH 0.3) was prepared by purchasing from JCC Korea.

Zeolite in a humid state was prepared and prepared in the same manner as in Example 2.

As shown in Table 2 below, each of the polyaluminum silicate solutions was prepared and its changes were observed.

<Table 2> Comparison results of PACS according to amount of zeolite and water added in moisture

Waste Aluminum Chloride Zeolite addition amount Amount of water added Remarks 1,000 g 60 g (6%) 106 g (10%) Gelled after 20 days 1,000 g 60 g (6%) 159 g (15%) Gelled after 30 days 1,000 g 60 g (6%) 212 g (20%) Not gelated 1,000 g 60 g (6%) 424 g (40%) Not gelated 1,000 g 60 g (6%) 742 g (70%) Not gelated 1,000 g 100 g (10%) 110 g (10%) Gelled after 1 day 1,000 g 100 g (10%) 165 g (15%) Gelled after 30 days 1,000 g 100 g (10%) 220 g (20%) Not gelated 1,000 g 100 g (10%) 440 g (40%) Not gelated 1,000 g 100 g (10%) 770 g (70%) Not gelated

As shown in Table 2 above, it was found that the gelation did not occur when dilute by adding 20% or more of water when adding 6-10 wt% of zeolite to waste aluminum chloride.

However, when water is added in excess of 70%, the concentration of polyaluminum chloride solution is too low, which leads to a problem of low efficiency, and even when the amount of zeolite is more than 10%, the dilution ratio must be increased to prevent gelation. The concentration of the aluminum chloride solution is too low, there is a problem that the efficiency is lowered.

Therefore, 6-10 wt% of zeolite is added and mixed with waste aluminum chloride, and water is diluted by adding 20-70 wt% of the mixture to the weight of the mixture. The efficiency was good and the effect was great.

Experimental Example 3 Comparative Experiment of Polyaluminum Chloride Solution with Addition of Zeolite Powder

A waste aluminum chloride solution (wasted AlCl ₃ solution; Al ₂ O ₃ 5.9%, pH 0.4) was prepared and purchased from JCC Korea.

Zeolite powder was prepared and prepared in the same manner as in Example 3.

3 g, 10 g, 15 g, 20 g, and 25 g of the prepared zeolite powder were added to 1,000 g of the prepared aluminum chloride solution, respectively, to prepare a polyaluminum silicate solution, and the changes thereof are shown in Table 3 below.

<Table 3> Comparative Results of PACS According to Addition of Zeolite Powder

Waste Aluminum Chloride Zeolite addition amount Remarks 1,000 g 3 g (0.3%) Not gelated 1,000 g 10 g (1.0%) Not gelated 1,000 g 20 g (2.0%) Not gelated 1,000 g 25 g (2.5%) Gelled after 30 days 1,000 g 30 g (3.0%) Gelled after 45 days

As shown in the results of Table 3 above, the gelation was not performed when the polyaluminum silicate solution was prepared by adding the zeolite powder up to 20 g, but it was found that the gelation proceeded when added to 25 g or more.

However, when preparing a polyaluminum chloride silicate solution by adding less than 3 g of zeolite, there is a problem that the effect of the polyaluminum chloride silicate solution is inferior. Therefore, when the zeolite powder is added to the waste aluminum chloride solution, It was found that the addition of 0.3 to 2% by weight to the gel does not proceed and the effect is high because of the high shelf life.

Experimental Example 4 Comparative Experiment of Polyaluminum Chloride Solution with Addition of Zeolite Powder and Water

A waste aluminum chloride solution (wasted AlCl ₃ solution; Al ₂ O ₃ 5.9%, pH 0.4) was prepared and purchased from JCC Korea.

Zeolite powder was prepared and prepared in the same manner as in Example 4.

As shown in Table 4 below, the polyaluminum chloride silicate solution was prepared, and the change thereof was observed.

<Table 4> Comparison results of PACS according to zeolite powder and water addition amount

Waste Aluminum Chloride Zeolite addition amount Amount of water added Remarks 1,000 g 30 g (3%) 103 g (10%) Gelled after 7 days 1,000 g 30 g (3%) 309 g (30%) Gelled after 30 days 1,000 g 30 g (3%) 412 g (40%) Not gelated 1,000 g 30 g (3%) 515 g (50%) Not gelated 1,000 g 30 g (3%) 1,030 g (100%) Not gelated 1,000 g 100 g (10%) 110 g (10%) Gelled after 7 days 1,000 g 100 g (10%) 330 g (30%) Gelled after 30 days 1,000 g 100 g (10%) 440 g (40%) Not gelated 1,000 g 100 g (10%) 550 g (50%) Not gelated 1,000 g 100 g (10%) 1,100 g (100%) Not gelated

As shown in Table 2 above, it was found that the gelation did not proceed when more than 40% of water was added to the waste aluminum chloride when 3-10 wt% of the zeolite powder was added.

However, when water is added in excess of 100%, there is a problem that the concentration of polyaluminum chloride solution is lowered and the efficiency is lowered. When the amount of zeolite added is more than 10% by weight, the dilution ratio must be increased, so the efficiency is inferior. have.

Therefore, 3-10% by weight of zeolite is added and mixed with waste aluminum chloride, and water is diluted by adding 40-100% by weight to the weight of the mixture. The efficiency was good, the effect was excellent.

Experimental Example 5 Comparative Experiment of Water Treatment Effect Using Polyaluminum Chloride Solution

A commercial aluminum polysilicate silicate solution was purchased and prepared.

Polyaluminum chloride silicate solution prepared by the method of Examples 1 to 4 of the present invention was prepared.

A conventional papermaking wastewater of pH 7 was prepared.

The conventional polyaluminum silicate solution prepared and the polyaluminum silicate solution of the present invention were treated in the prepared paper wastewater to observe the flocculation effect and sedimentation rate in each case.

The results are shown in Table 5 below.

Table 5 Effect test results of polyaluminum silicate solution

division usage Coagulation effect Sedimentation rate Example 1 800 ppm Prize speed Example 2 800 ppm Prize speed Example 3 800 ppm Prize speed Example 4 800 ppm Prize speed Conventional PACS 800 ppm Ha Slow

As shown in Table 5 above, the water treatment using the polyaluminum chloride silicate solution of Examples 1 to 4 of the present invention is superior to the case of water treatment using the conventional polyaluminum silicate solution, and the aggregation effect is also excellent. The sedimentation rate was also fast.

Therefore, it can be seen that the effect of the polyaluminum silicate solution prepared using the waste aluminum chloride of the present invention is superior to that of the conventional polyaluminum silicate solution.

According to the present invention, a method for producing a polyaluminum chloride silicate solution having low storage cost and excellent storage property by using a waste aluminum chloride solution is provided.

In addition, the present invention provides a polyaluminum chloride silicate solution that can be used as a water treatment agent, a papermaking size agent, and the like. In particular, when used as a water treatment agent, a polyaluminum chloride silicate solution having a large flocculating effect and a fast settling rate effect is provided.

Claims (8)

In the method for producing a polyaluminum chloride silicate solution, A first step of preparing a waste aluminum chloride solution, A second step of manufacturing a zeolite or zeolite powder in a moisture state by using aluminum dross; The polyaluminum chloride silicate solution is prepared by a third step of mixing and mixing the zeolite prepared in the second step into the waste aluminum chloride solution prepared in the first step. Method for producing a polyaluminum chloride silicate solution using waste aluminum chloride solution. The method of claim 1, The zeolite of the second step is a first step of producing an aluminum material mixture by mixing water into an aluminum material (aluminum dross) 3-6 times the weight of the aluminum material, A second step of preparing an alkali salt solution by adding 1-5% by volume of sodium silicate solution to the caustic soda solution relative to the volume of caustic soda solution, and mixing the caustic soda solution, A third step of dissolving the alkali salt solution prepared in the second step into the aluminum mixture of the first step in a ratio of 80 to 120 g per 100 g of the aluminum material of the first step, A fourth process of filtering the solution of the third process, The sodium silicate solution was added to the filtrate of step 4 at a rate of 70 to 100 ml per 100 g of the aluminum material of the first step, mixed and stirred. The stirred solution was filtered to store the filtrate separately. Characterized by consisting of a fifth process of collecting and manufacturing a zeolite in a moist state, or a zeolite powder by naturally drying the zeolite in a moisture state, Method for producing a polyaluminum chloride silicate solution using waste aluminum chloride solution. The method of claim 1, In the case of using the moist state zeolite in the preparation of the polyaluminum chloride silicate solution of the third step, 1 to 5% by weight of the zeolite in the moisture state prepared in the second step is mixed with the waste aluminum chloride solution prepared in the first step. Characterized in preparing a polyaluminum chloride silicate solution,  Method for producing a polyaluminum chloride silicate solution using waste aluminum chloride solution. The method of claim 1, In the case of using the moistened zeolite in the preparation of the polyaluminum chloride silicate solution of the third step, 6-10 wt% of the zeolite in the wet state is mixed with the waste aluminum solution, followed by mixing water with 20-70 wt% of the mixture. Characterized in that the addition and mixing to prepare a polyaluminum silicate solution Method for producing a polyaluminum chloride silicate solution using waste aluminum chloride solution. The method of claim 1, When the zeolite powder is used to prepare the polyaluminum chloride silicate solution of the third step, the polychlorinated solution is mixed with 0.3 to 2% by weight of the zeolite prepared in the second step to the waste aluminum chloride solution prepared in the first step. Characterized in preparing an aluminum silicate solution,  Method for producing a polyaluminum chloride silicate solution using waste aluminum chloride solution. The method of claim 1, In the case of using the zeolite powder in the preparation of the polyaluminum chloride silicate solution of the third step, 3 to 10% by weight of zeolite in a moist state is mixed with the waste aluminum solution, and then 40 to 100% by weight of water is added to the mixture. Characterized in that to prepare a polyaluminum silicate solution by mixing Method for producing a polyaluminum chloride silicate solution using waste aluminum chloride solution. Prepared by the method of any one of claims 1 to 6, Polyaluminum chloride silicate solution using waste aluminum chloride solution. The method of claim 7, wherein Characterized in that it is used as a water treatment agent or a paper size agent, Polyaluminum chloride silicate solution using waste aluminum chloride solution.

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