KR100481286B1 - Method of preparing liquid calcium chloride using shell - Google Patents

Abstract

The present invention relates to a method for producing liquid calcium chloride using a shell, and to a method for producing liquid calcium chloride for medical use and snow removal using a shell such as a cockle, a clam, a book, a shellfish, and the like.

The present invention provides a method for producing liquid calcium chloride using the shell, the reaction step of dissolving the shell in hydrochloric acid in the reaction tank; A neutralization step of adding CaO or CaCO ₃ to the calcium chloride mixture solution (A) obtained in the reaction step; A first step of purifying potassium permanganate (KMnO ₄ ) to the calcium chloride mixed solution (B) passed through the neutralization step; Refining two steps of adding hydrogen peroxide (H ₂ O ₂ ) and activated carbon to the calcium chloride mixed solution (C) that has passed through the first refining step; And it provides a method for producing calcium chloride comprising the step of filtering the calcium chloride mixed solution (D) passed through the purification step 2.

The production method of the present invention is inexpensive using a shell which is a natural marine resource, and has an excellent effect of mass-producing liquid calcium chloride of high purity.

Description

Method for preparing liquid calcium chloride using a shell {METHOD OF PREPARING LIQUID CALCIUM CHLORIDE USING SHELL}

The present invention relates to a method for producing liquid calcium chloride using a shell. More particularly, the present invention relates to a method for preparing liquid calcium chloride consisting of a step of neutralizing, purifying, and filtration by reacting a shell such as a pinnacle, clam, batter, oyster shell and shellfish with hydrochloric acid.

Generally, liquid calcium chloride (CaCl ₂ ) is mixed with various drying agents, for snow removal, for medical use, for electronic materials, and with concrete, to prevent freezing, to manufacture decolored coal, for dehydration of solvents, for snow removal, and for food. It is used as an additive or the like.

Conventional calcium chloride is a flake type (Flake type), there was a problem in that it is inconvenient to use and corroded when used in metal. In recent years, the problem has been solved by spraying liquid calcium chloride directly on the road to prevent freezing.

As a manufacturing method of calcium chloride, there existed the industrial manufacturing method using the ammonia-soda method (Solvay method). This was done by a chemical synthesis method such as concentrating the waste solution of the ammonia distillation column, or producing calcium chloride as a by-product in preparing sodium chlorate by the lime method, in which case calcium chloride is produced in the form of by-products. There was a problem that the purity was somewhat lower.

As an attempt to use a shellfish containing a large amount of natural calcium compounds, rather than the method of industrial production as described above, Korean Patent Laid-Open No. 2001-44280 (Method for producing calcium lactate using shell shell) , Korean Patent No. 265976 (Calcium Chloride Solution Manufacturing Equipment for Road Snow Removal),

In addition, Korean Patent Laid-Open Publication No. 2002-23845, "Manufacturing process of high purity calcium chloride using shellfish", discloses a method of dissolving a shell in hydrochloric acid, adding ammonia to adjust pH, and removing impurities through precipitation. However, the method has a problem that it is difficult to mass-produce due to foaming by carbon dioxide generated by the reaction of hydrochloric acid and shells.

The present inventors have continually researched to produce liquid calcium chloride using shells containing a large amount of natural calcium compounds, and the object of the present invention is to provide a simplified method for producing liquid calcium chloride with low cost and high purity. It is done.

In addition, the present invention shortens the manufacturing process of liquid calcium chloride by spraying hydrochloric acid by spraying to remove bubbles generated by the reaction of hydrochloric acid and shells, it is possible to produce in large quantities, the high-purity of liquid calcium chloride It is an object to provide a manufacturing method.

In order to solve the above technical problem, a liquid calcium chloride manufacturing method will be described.

The present invention is a method for producing liquid calcium chloride using a waste shell,

A reaction step of dissolving the shell in hydrochloric acid in the reactor; A neutralization step of adding CaO or CaCO ₃ to the calcium chloride mixture solution (A) obtained in the reaction step; A first step of purifying potassium permanganate (KMnO ₄ ) to the calcium chloride mixed solution (B) passed through the neutralization step; Refining two steps of adding hydrogen peroxide (H ₂ O ₂ ) and activated carbon to the calcium chloride mixed solution (C) that has passed through the first refining step; And it provides a method for producing a liquid calcium chloride using a shell characterized in that it comprises the step of filtering the calcium chloride mixed solution (D) passed through the purification step.

Hereinafter will be described in detail step by step the manufacturing method of the present invention.

[Step 1: Reaction stage (reactor stage)]

This step is a step of dissolving the shells (knapsack, shellfish, confectionery, clam, etc.) in hydrochloric acid, by putting the shells and hydrochloric acid in the reactor, dissolving the shells in hydrochloric acid to prepare a calcium chloride mixture (A) . Before the reaction step, it is preferable to wash the shell with water, and then pulverized by adjusting the particle size according to the use, and then put into the reactor.

In this step, the shell impurities are precipitated without dissolution, and the calcium component and hydrochloric acid of the shell react to form a calcium chloride mixture solution. In this step, it is preferable to dissolve until the concentration of calcium chloride reaches 25% by weight.

Scheme 1: shell (CaCO ₃ + impurity) + hydrochloric acid (HCl) → calcium chloride mixture (CaCl ₂ ) + H ₂ CO ₃ (H ₂ CO ₃ ↔ H ₂ O + CO ₂ ) + water-soluble impurities + CO ₂ ↑

In this step, hydrochloric acid is added to produce calcium chloride by reacting with the calcium carbonate compound component, which is the main component of the shell. At this time, hydrochloric acid also reacts with impurities present in the shell to generate an organic material, and the organic material is composed of a trace amount of chlorine compound, and the remaining chlorine compound is impurity at the same time the pH is adjusted during neutralization in the second step. This is to be purified.

However, as the shell is dissolved in hydrochloric acid, a large amount of bubbles (bubbles) are generated by carbon dioxide, which requires a lot of reaction (dissolution) time, resulting in a long process, and difficulty in increasing the concentration. There was a problem that it was almost impossible.

In order to solve the above problems, it was found that in this reaction step, after putting the shell inside the reactor, it is preferable to prepare a calcium chloride mixed solution by spraying hydrochloric acid on the shell by spraying. In particular, it is particularly preferable that the dispensing equipment at the time of dissolution is installed in the lid portion of the upper portion of the reaction vessel rather than the side of the reaction vessel. Spraying hydrochloric acid by spraying removes bubbles (bubbles) by carbon dioxide generated at the same time as the supply of hydrochloric acid, which is characterized in that continuous operation can be performed.

The hydrochloric acid added in this step is preferably 18 to 20 W / V% in terms of work efficiency. In this step, hydrochloric acid is preferably dissolved until the concentration of calcium chloride is 25 W / V%.

[Second Step: Neutralization Step of Adding CaO or CaCO ₃ ]

This step is to adjust the pH by adding quicklime (CaO) or CaCO ₃ to the calcium chloride mixture (A). The calcium chloride mixture is a solution of strong acidity (pH of 1-2). In this strongly acidic solution, it is not possible to remove various metallic substances dissolved by hydrochloric acid and remain as impurities. Therefore, these various metallic substances can be removed from the metal aquatic product M (OH) ₂ · (OH) _{3 (} where M is a metal ion). Step of adjusting the pH of the calcium chloride mixture solution to precipitate out in the form of).

In the neutralization step by CaO or CaCO _{3 in} this step, bubbles (bubbles) due to the generation of carbon dioxide can be removed through the ventilator.

In the case of adding calcium oxide obtained industrially or from minerals other than quicklime obtained from the shell, there is a problem that the calcium chloride mixture solution becomes cloudy.

[3rd step: 1st step of purification by adding potassium permanganate (KMnO4)]

This step is a purification step of adding potassium permanganate (potassium permanganate) to the calcium chloride mixture (B) passed through the neutralization step. The potassium permanganate is a powerful oxidant to oxidize and remove Fe, Mn, Mg, Al, K and the like impurities of the shell.

Potassium permanganate is an oxidizing agent and its equivalent varies depending on the degree to which Mn is reduced. By way of example, when Mn 2+ is reduced, its equivalent is 1/5 Mol (31.6 g). That is, MnO4- + 8H ++ 5e (potential coefficient) → Mn2 ++ 4H2O or 2KMnO4 → K2O + 2MnO + 5O.

In particular, the hydrochloric acid solution used when preparing the calcium chloride in the present invention has the following reaction characteristics, it is necessary in the purification step to avoid this point. 2KMnO ₄ + 16HCL → 2KCl + 2MnCl ₂ + 5Cl ₂ + 8H ₂ O

[4th step: 2nd step of purification by adding hydrogen peroxide and activated carbon]

This step is a step of adding hydrogen peroxide (H ₂ O ₂ ) and activated carbon (activated carbon) to the calcium chloride mixture (C) passed through the first step of purification. In this step, hydrogen peroxide acts as a strong oxidant to decompose and remove water-soluble impurities such as protein and organic substances, and activated carbon improves APHA by adsorbing, deodorizing and decolorizing organic substances. In this step it can be adjusted by adding hydrochloric acid so that the pH of the calcium chloride mixture solution is 5.5-7.0. This not only improves the efficiency of the two stages of purification to increase the purity, whiteness, etc. of the liquid calcium chloride, but also because the demand for the liquid calcium chloride is mostly used for which the pH is required to be neutral.

[Step 5: Filtration Step]

This step is a step of filtering the calcium chloride mixture solution (D) passed through the purification step 2. There is no particular limitation on the method of filtration, but filtration using a pressure filter or the like is preferable.

Referring to Figure 3 will be described a method for producing a liquid calcium chloride of the present invention. First, the shell injected into the reactor 3 is dissolved in hydrochloric acid supplied by the hydrochloric acid storage tank 1 to prepare a calcium chloride mixed solution. In particular, the hydrochloric acid is preferably sprayed through a hydrochloric acid spray apparatus mounted on top of the reactor. Gas such as carbon dioxide generated by the reaction is transferred to the gas scrubber tower 8, and the calcium chloride mixed solution is transferred to the shell dissolution tank 2 through a transfer pipe. Some of the calcium chloride mixed solution transferred to the shell dissolution tank 2 is transferred to the reaction tank 3 again, and a portion of the calcium chloride mixed solution is transferred to the shell reaction tank 4. Through the supply of calcium oxide in the calcium oxide storage tank 7, the pH of the calcium chloride mixed solution is adjusted. In addition, a calcium oxide storage tank and optionally a calcium carbonate storage tank may be provided. The calcium chloride mixed solution passed through the reaction tank is purified by reaction with potassium permanganate, hydrogen peroxide and activated carbon supplied through a tank provided separately, and then transferred to the calcium chloride storage tank 5 through filtration by a filter press. The liquid calcium chloride by this can be obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, an Example is for illustration of this invention and does not limit this invention only to the following Example.

Example 1

Hydrochloric acid solution is added to the reaction vessel with 1000 kg of washed water, and 1.88 m ³ of 18 W / V% hydrochloric acid solution is added until the calcium chloride concentration reaches 25 W / V%. The calcium chloride mixture solution was transferred to a neutralization tank, 40 kg of CaO was added to adjust the pH to 5.5, and then 50 g of potassium permanganate (KM) was added to the calcium chloride mixture solution passed through the neutralization tank to oxidize impurities. Liquid calcium chloride 5m ³ was prepared by adding 80 g of the purified calcium chloride mixed solution H ₂ O ₂ solution and 5 kg of activated carbon and finally filtering with a pressure filter.

Example 2

A liquid calcium chloride was prepared in the same manner as in Example 1, except that 1000 kg of washed pinch was placed in a reactor and sprayed by spraying hydrochloric acid solution until the concentration of calcium chloride was 25 W / V%.

Example 3

Liquid calcium chloride was prepared in the same manner as in Example 1, except that 70 g of CaCO ₃ was added instead of CaO.

Table 1 below shows the results of investigating the components of shellfish.

The liquid calcium chloride prepared in Example 1 was analyzed using an inductively coupled plasma atomatic emission spectrometer (IPC), and the results are shown in Table 2 below.

Table 1 Components of Shellfish

Calcium carbonate Other ingredients Cock 95-97 wt% 3 ~ 4% protein, trace amount of Al, Fe, Mg Clam 95-96 wt% 4 ~ 5% protein, trace amount of AL

Table 2 Table of IPC Analysis of Liquid Calcium Chloride

Concentration in ppm ingredient Al As Mn Pb PO ₄ ^3- SO ₄ ^2- Example 1 1.39 Not detected 4.86 Not detected Not detected 359.90 Example 2 0.75 Not detected 2.7 Not detected Not detected Not detected Example 3 0.90 Not detected 2.0 Not detected Not detected Not detected

[Table 3] Physical Properties of Liquid Calcium Chloride

Example 1 Example 2 Example 3 Ingredients and Content (W / V%) CaCl _2: 18.5, Fe: 0.005Mg: Not detected CaCl ₂ : 18.0, Fe: 0.005, Mg, Al: Not detected CaCl ₂ : 20.0, Fe: 0.005, Mg, Al: Not detected Exterior transparent transparent transparent Purity% 18.5% 18.0 18.9 importance 1.160 1.158 1.164 Absorbance 4 3 2 pH 5.5-7.0 6.5 7.0

In the above, the appearance was measured using a transparent Nessler Tube. Purity was measured by EDTA quantitation and Hydometer Method, specific gravity was measured by a Densimeter Hydrometer Method Density Meter at 20 ° C., and absorbance was measured using a colorimeter.

As described above, the manufacturing method of the present invention is inexpensive by utilizing the shell, which is a natural marine resource, and has an excellent effect of producing a high purity liquid calcium chloride through a simplified process.

In addition, the manufacturing method of the present invention has an excellent effect that the liquid calcium chloride shortens the process time and enables mass production by removing the carbon dioxide bubbles generated by the reaction of the hydrochloric acid and the shell through the spray injection of hydrochloric acid. .

1 illustrates a manufacturing process of the present invention.

Figure 2a shows the results of X-ray diffraction analysis of commercially available liquid calcium chloride.

In addition, 2b shows the results of X-ray diffraction analysis of the calcium carbonate prepared according to Example 1 of the present invention.

Figure 3 shows a manufacturing process of the liquid calcium chloride.

[Description of Symbols in Drawing]

1. hydrochloric acid storage tank 2. shell melting tank

3. Shell reaction tank 4. Shell reaction tank

5. Liquid Calcium Chloride Storage Tank 6. Dilution Tank

7. Calcium oxide storage tank 7 '. Hydrochloric acid metering tank

8. Gas scrubber

Claims (4)

A reaction step of dissolving the shell in hydrochloric acid in the reactor; A neutralization step of adding CaO or CaCO ₃ to the calcium chloride mixture solution (A) obtained in the reaction step; A first step of purifying potassium permanganate (KMnO ₄ ) to the calcium chloride mixed solution (B) passed through the neutralization step; Refining two steps of adding hydrogen peroxide (H ₂ O ₂ ) and activated carbon to the calcium chloride mixed solution (C) that has passed through the first refining step; And filtering the mixed calcium chloride solution (D) after passing through the purification step 2. Method for producing a liquid calcium chloride comprising a. The method of claim 1, The reaction step is a method for producing a liquid calcium film, characterized in that to prepare a calcium chloride mixed solution by spraying and supplying hydrochloric acid to the shell inside the reactor. The method of claim 1, Hydrochloric acid added in the reaction step is a method for producing a liquid calcium chloride, characterized in that 18 ~ 20W / V%. The method of claim 1, CaO or CaCO ₃ in the neutralization step is added so that the pH of the calcium chloride mixture solution is 10.0 or more, and hydrochloric acid is added to the pH so that the pH is 5.5 ~ 7.0 in the second purification step.