KR880001350B1 - Chemical active water solution and solid containing fe++ - Google Patents

Abstract

THE water solution and solid, impregnated and dried, having chemical activity of deodorization, sterilization, conservation of freshness and condensation of contaminants are composed of stable Fe(II) ion over 0.15 wt.% in solution, and L-ascorbic acid over 2.0 wt.% per 100 wt. % of Fe(II) ion.

Description

Chemically active aqueous solutions and solids containing bivalent ions

1 to 4 are graphs showing test results in Example 1. FIG.

5 is a graph showing test results in Example 2. FIG.

6 is a graph showing the test results in Example 3. FIG.

The present invention relates to a novel aqueous solution which performs various chemical functions such as deodorization, sterilization, maintenance of freshness of food and aggregation of contaminated substances (contaminated and turbid substances). The present invention relates to an aqueous solution containing a stabilized state and a solid material obtained by impregnating and drying the aqueous solution.

Iron (II) (ferric iron) compounds, such as ferrous sulfate, have a wide range of uses, but, as is well known, when left in the form of an aqueous solution, ferric ions are easily oxidized by dissolved oxygen or air to give a tan It has the property of causing precipitation by changing to.

In order to prevent oxidation of ferric ions in aqueous solution, it is known to add hydroxy amine, tin compound, etc. as a reducing agent. However, since these substances are highly toxic to humans, the use of aqueous solutions containing ferric ions Is being limited.

The present invention is to provide an aqueous solution containing stabilized ferric ions and to provide a novel use of an aqueous solution containing stabilized ferric ions.

The present inventors have conducted various studies on stabilization of ferric ions in an aqueous solution, and surprisingly, by adding a small amount of L-ascorbic acid, the dissolved ferric ions can be stabilized as they have their effective activity. And the aqueous solution containing the ferric ions stabilized by this L-ascorbic acid, the ferric ion which does not contain L-ascorbic acid by the cooperative action of L-ascorbic acid and the ferric ion. The aqueous solution containing exhibits an unusual chemical action that cannot be denatured, yielding an aqueous solution that can be applied to a wide range of applications, and the L-ascorbic acid and iron (II) obtained by drying the aqueous solution after impregnation with a solid material. The solid substance containing the compound is found to have a specific chemical action as in the case of the aqueous solution, and the present invention I completed it in early.

According to the present invention, a ferric ion and L-ascorbic acid are contained. The ferric ion is a value in terms of metal iron, and is present in an aqueous solution at a concentration of 0.15% by weight or more, and L-ascorbic acid is used as metal iron. There is provided a chemically active aqueous solution, which is present in a ratio of 2.0 parts by weight or more with respect to 100 parts by weight of the ferric ions represented by the converted value.

The aqueous solution of the present invention is easily prepared by dissolving the iron (II) compound and L-ascorbic acid in water.

As the iron (II) compound, any one can be used as long as it can dissolve in water to produce ferric ions. For example, ferrous sulfate ferrous chloride, ferrous embrittlement, ferrous iodide, and nitric acid In addition to the water-soluble iron (II) salts of inorganic acids, such as ferrous iron, water-soluble iron (II) salts of organic acids, such as a ferrous iron, ferric malic acid, and ferric fumarate, etc. are mentioned.

The concentration of the ferric ion in the aqueous solution is generally 0.15% by weight or more, preferably 0.3% by weight or more, in consideration of the specific chemical activity of the aqueous solution, and in terms of iron, and the upper limit thereof is iron (II). Is the solubility of the compound.

The amount of L-ascorbic acid added is 2.0 parts by weight or more based on 100 parts by weight of the ferric ions represented by the value in terms of metal iron present in the aqueous solution, and the upper limit is not particularly limited, but from an economic point of view It is preferable to set it as 30 weight part or less from a viewpoint, Preferably it is 3-10 weight part.

When the addition amount of L-ascorbic acid is less than 2 parts by weight with respect to 100 parts by weight of the ferric ions, it is not preferable because the stabilizing effect on the ferric ions is small.

In the aqueous solution containing the ferric ions added with L-ascorbic acid according to the present invention, the ferric ions are stabilized in the active state.

Therefore, even if this aqueous solution is brought into contact with air for a long time, no substantial precipitation is formed.

In addition, the aqueous solution of the present invention can be used by impregnating an absorbent solid material.

In this case, the solid substance impregnated with the aqueous solution is suitably dried, and the L-ascorbic acid and the iron (II) compound are supported on the solid substance.

The combination of L-ascorbic acid and iron (II) compounds supported on such a solid substance also exhibits specific chemical activity as seen in aqueous solution.

The aqueous solution of the present invention exhibits various specific chemical activities as compared with the usual aqueous solution containing ferric ions, but as the activity, odorous substances containing sulfur or nitrogen, such as hydrogen sulfide and methyl mercaptan It has shown that it has a remarkably high deodorizing effect with respect to ammonia, trimethylamine, etc.

In an aqueous solution for the purpose of this deodorizing effect, L-ascorbic acid is 2-30 parts by weight with respect to 100 parts by weight of iron (II), preferably 3-10 parts by weight. In this deodorizing aqueous solution, the concentration of the total amount of L-ascorbic acid and the iron (II) compound in the aqueous solution is 0.1-30% by weight, preferably 1.0-20% by weight.

In order to make this aqueous solution a solid deodorant, it can be dried and impregnated with solid materials, such as paper, synthetic cloth, a nonwoven fabric, and a porous filler.

In this case, the drying treatment may be omitted in some cases. Examples of the porous filler include activated carbon, zeolite, bentite, kaolin, pearlite, sepiolite, silicon earth, silica, alumina, and the like, and the shape thereof may be arbitrarily selected from powder form and granule shape. The total amount of L-ascorbic acid and iron (II) compound supported on the solid material is about 0.5-20 parts by weight as a solid content with respect to 100 parts by weight of the solid material.

In case of paper or non-woven fabric supporting L-ascorbic acid and iron (II) compound, it may discolor when left in the air for a long time, but in this case, thiosulfate such as sodium thiosulfate or sodium ionate such as sodium itionate Can be prevented by coexisting in an appropriate amount, such as about 1/10 or less of the total amount of L-ascorbic acid and the iron (II) compound.

The deodorant composed of an aqueous solution or a solid substance containing the L-ascorbic acid and the iron (II) compound can be applied to the purpose of removing odors such as toilets, waste bins, refrigerators and drains.

In the method of application as a deodorant, in the case of an aqueous solution, there are methods of spraying and washing the source of malodor, and in the case of a solid state, in addition to the method of directly administering to the source of malodor, the solid deodorant is malodorous. How to put it in the space where there is.

The deodorant may be used by being contained in a part of sanitary material such as a diaper or menstrual band.

As a 2nd specific activity of the aqueous solution of this invention, it is bactericidal and has the effect of freshness maintenance with respect to foodstuffs. When the aqueous solution of the present invention is applied to fresh foods such as vegetables, fruits, meat, and processed foods thereof, the freshness of these foods can be extended for a considerable period of time.

As an application method in this case, there exists a method of apply | coating or spraying aqueous solution with food, etc., or immersing food in aqueous solution.

In addition, this aqueous solution can be dried after being impregnated in a solid material such as paper, synthetic paper, nonwoven fabric, porous filler and the like to maintain a freshness in a solid state as in the case of the deodorant.

Regarding the application method of the above-mentioned solid state freshener, for example, in the case of sheet or film state, the food may be packaged using the sheet or film, and in the case of powder or granule state, these may be appropriately applied. May be mixed with the drug.

The above-mentioned aqueous solution or solid substance containing L-ascorbic acid and iron (II) compound is used as a lead retaining agent, but this lead holding effect is strong due to the combination of L-ascorbic acid and ferric ions. It is due to bactericidal action. The composition containing L-ascorbic acid and ferric ions can also be used as a fungicide against E. coli and other common bacteria.

Another specific activity of the aqueous solution of the present invention is that it has an effect of promoting aggregation of contaminated substances (contaminated and turbid substances). With respect to water containing contaminants, when L-ascorbic acid and ferric ion are added, the contaminants form precipitates and settle.

The aqueous solution used for the purpose of such a water treatment agent is about 0.01-20 weight% in the density | concentration of the total amount of L-ascorbic acid and a ferric compound.

In addition, the coagulant effect can be promoted by adding a small amount of colloidal dispersant such as zeolite, bentite, silica follower and acid clay to the aqueous solution.

The water treatment agent containing this L-ascorbic acid and an iron (II) compound is very excellent in the aggregation effect of organic substances, such as humic acid, sodium lignin sulfonate, and alkali lignin.

로 변화되는 것에 기인하는 것이라고 생각되어 진다.A solution or solid state composition comprising L-ascorbic acid and divalent ions of the present invention exhibits various specific activities as described above, but their activity is in the presence of L-ascorbic acid. Super Oxide has a stronger oxidizing power than oxygen in the molecular state due to the action of the ferric ion in the molecule.

It is thought that it is due to the change.

The reaction in this case can be represented by the following equation.

The aqueous solution containing L-ascorbic acid and ferric ions of the present invention can be applied to a conventionally known use for aqueous solutions containing divalent ions, in addition to various specific purposes as described above. will be.

An embodiment of the present invention will be described in detail as follows.

Example 1

L-ascorbic acid was dissolved in an aqueous solution of ferrous sulfate (51.7 g Fe / l) in the range of up to 5 g per liter. 100 ml of each aqueous solution was taken in a 100 ml beaker, placed on a watch plate, and left open. The change of the color of the aqueous solution and the formation of precipitates with the naked eye was observed over time. The test results are shown in Table 1 below.

[Table 1]

Changes over Time of Ferrous Sulfate with L-ascorbic Acid

In addition, the chromaticity was measured by UV-300 about the ferrous sulfate aqueous solution which added each L-ascorbic acid. The results are shown in FIGS. 1 to 4. In each figure, the absorption spectrum for every day passed is shown. The amount of L-ascorbic acid added is 0.5g / l, 1g / l, 2g / l in FIGS. 1 to 3, respectively, and the amount of L-ascorbic acid added for comparison in FIG. 4 is 0. to be.

From the result of FIG. 1, 0.5g was added, but it was almost stable until after 7 days, but after 8 days, ferrous sulfate aqueous solution caused a change over time.

And as can be seen from FIGS. 2 to 3, this is markedly stabilized with an increase in the amount of L-ascorbic acid added, and in the case of FIG. 3 (additional 2 g), little change occurs after 21 days. Able to know.

In contrast, in the case of FIG. 4 in which the amount of L-ascorbic acid added is 0, the stabilization of the absorption spectrum is not seen, and the change with time is obvious.

Example 2

100 ml of an aqueous solution of 15% ferrous sulfate, 2.5% magnesium oxide, 0.4% acidic clay, and 0.4% natural zeolite (above% by weight) is diluted to 1 l with hydrochloric acid, and the amount of addition is changed in the range up to 20 g. -Flocculant containing ascorbic acid was prepared.

50 mg/l인 후민산액을 조제하였다.On the other hand, COD as the liquid to be treated

A humic acid solution of 50 mg / l was prepared.

49 ml of the treatment solution was taken in a beaker, stirred at 150 r.p.m, and then 10 ml of each of the coagulants described above was added, and the pH was then adjusted to 7.0 with hydrochloric acid or sodium hydroxide solution.

After adjusting the pH, the mixture was stirred at 150 r.p.m for 5 to 10 minutes and then at 60 r.p.m for 15 minutes. After completion of stirring, the resultant was centrifuged and filtered with a filter paper of 5C to prepare a sample, and the organic matter removal rate and residual iron were measured.

The result is shown in FIG. 5, and it can be seen from this result that the removal rate of humic acid is considerably improved by the addition of L-ascorbic acid up to 10 g / l.

In addition, the residual iron was air oxidized to neutral alkali (pH 7-8) in neutral to remove iron according to a conventional method.

Example 3

(A). Preparation of L-ascorbate

25.7 g of ferrous sulfate sulfate (molecular weight: 278.03) was dissolved in ion-exchanged water to make 100 ml, and 0.5 g of L-ascorbic acid was added to dissolve to prepare an aqueous solution for sterilizing iron ascorbic acid. .

(B). Sterilization Experiment

①. Water to be treated

On July 27, 1982, water from Ibaragigen Ushigu Wetland was collected from the forest near the village.

②.Sterilization test method

100 ml of water to be treated is taken in a 100 ml beaker for quick dry heat sterilization, and vigorously stirred. To this, 1 ml of a 1-100-fold dilution of the aqueous solution of iron-ascorbic acid is added, and 5 minutes, 10 minutes, 15 minutes and A sample after 30 minutes was taken, and the culture test was carried out using a desuccyclate medium by the method shown below to determine the number of Escherichia coli groups.

③ Culture test method

When 1 or more samples of E. coli were expected to be present in 1 ml of the sample, 9 ml or 99 ml of phosphate buffered dilution water was added to the 1 ml and diluted. Dilution was carried out as needed to prepare a dilution sample in which the E. coli group was collected in the range of 30-300 / ml after incubation.

Next, 1 ml of this sample is collected in a sterile chamois, and after heating and dissolving, about 10 ml of descyclate medium maintained at about 48 ° C. is added, shaken, and mixed well with the feed.

Once the mixture has spread throughout the sterile chaire, it is left to horizontal to solidify. Once the mixture has solidified, add 5 to 10 ml of descyclate medium to cover the entire coagulation surface and coagulate in an overlapping layer. After coagulation, the sterilized saare is placed in the reverse direction into the incubator and incubated at 36 ± 1 ° C. for 18 to 20 hours. The number of formal populations representing red to magenta generated in the medium is counted, and the average value is calculated and expressed as the number in 1 ml of the sample. In the case of a diluted sample, 30 to 300 population groups were obtained and the number in 1 ml of the sample was obtained.

(C) Sterilization test results

The percentage (%) of E. coli counts in each sterilized sample to the E. coli counts of untreated water was obtained to obtain the remaining percentage of viable cells. The relationship between the sterilization treatment time (minutes) and the remaining percentage of viable bacteria by L-ascorbic acid withdrawal solutions of various concentrations is shown in FIG. From the results of the chart, the concentration of iron ascorbate is about 0.01%, but the bactericidal effect is almost insignificant even after 30 minutes of contact time, but when it is more than 0.1%, the effect is remarkable. An improvement in bactericidal power can be seen. Such an effect cannot be expected in an iron (II) solution, and no bactericidal effect is exhibited at this concentration of ascorbic acid. As described above, it can be seen that the addition of iron ascorbate of about 0.1% enables sterilization of the E. coli group without exhibiting secondary effects, and the extremely ineffective effect can be widely used for many purposes.

Example 4

(A). Preparation of antiseptic preservatives impregnated with L-ascorbate.

27.5 g of ferrous sulfate hexahydrate (molecular weight 278.03) was dissolved in water to make 100 ml, and then 0.5 g of L-ascorbic acid was added to dissolve to prepare an aqueous solution of ferrous L-ascorbic acid solution.

Next, this stock solution was diluted 5 times with water, and it was sprayed onto the whole surface of the graph paper (33.2 cm x 24 cm) and sprayed with a nebulizer. Dried.

(B). Leading Maintenance Test

Along with the graph area impregnated with L-ascorbate, the graph area which was not treated for comparison was prepared, and 220 g of freshly prepared plate fish jelly, 85 g of frozen angle shrimp, Seal 120 g of grapes or 120 g of giant grapes, respectively, and seal them. At room temperature (20 ° C), the changes of the freshness of each food and the occurrence of decay (mold, decay) were observed. Is shown in Table 2.

According to the present invention from the results of Table 2, it can be seen that the plate-shaped fish jelly, seedless grapes, and grape grape grapes can be endured for about seven days in total compared with the comparative example at room temperature.

In addition, according to the present invention also frozen frozen shrimp, it can be seen that it can withstand about five days long compared to the comparative example.

[Table 2]

Example 5

27.5 g of ferrous sulfate hexahydrate (molecular weight 278.03) was dissolved in water to make 100 ml, and 0.5 g of L-ascorbic acid was added thereto to dissolve to prepare an aqueous solution of ferrous L-ascorbic acid solution.

Next, the stock solution of L-ascorbic acid aqueous solution was diluted 10 times with water to prepare a liquid deodorant. Next, 10 g of chicken dung were put into two strength bottles (for 100 ml), 50 ml of the above-mentioned liquid deodorant was added to one side and left for 24 hours in a constant temperature room at 37 ° C. After standing, the generated gas in each strength bottle was extracted with 20 l of pure air and collected in a bag to measure the amount of hydrogen sulfide, methyl mercaptan and ammonia in each of the two gases (deodorized and untreated). The results are shown in Table 3.

Example 6

In Example 5 to granular activated carbon (granule diameter 1.5-2.5 mm prepared by a conventional method by drying after extrusion molding a mixture containing 20 parts by weight of commercially available granular powder activated carbon, 20 parts by weight of zeolite and 60 parts by weight of bentite) After impregnating 15 wt% of the prepared aqueous solution of iron-ascorbate, it was dried at room temperature for 24 hours to prepare a granular deodorant.

On the other hand, 20g of chicken poultry was added to a century bottle (for 100 ml), 100 ml of purified water was added thereto, and left for 24 hours in a constant temperature room at 37 ° C.

Next, 20 g of the granular deodorant described above was filled into a glass tube, and 20 l of malodorous source gas in the bag was passed at a flow rate of 2-3 l / min, and the gas was collected in a bag, and the odor component therein was measured. . The results are shown in Table 3. From the results in Table 3, it can be seen that the liquid or granular deodorant of the present invention shows a very good deodorizing effect against any of hydrogen sulfide, methyl mercaptan and ammonia.

[Table 3]

(Note) The odor component was measured as follows.

One). Hydrogen sulfide and methyl mercaptan gas chromatography were used for quantification.

2). ammonia

After collecting with an ammonia absorbing liquid (1/50 NH ₂ SO ₄ liquid), the amount thereof was quantified by absorbance photometry.

Example 7

Dilute the aqueous solution of ferric L-ascorbate prepared in Example 5 (after 3 months of manufacture) twice with tap water, and spray the solution in a predetermined amount of 15 cm diameter filter paper (Toyo Filter Paper No. 5c, Japan). It was dried to prepare a paper-based deodorant with an iron dry weight of ascorbate (A) 0.38g (B) 0.39g (C) 0.37g (D) 0.48g.

On the other hand, dilute 25% aqueous ammonia in 4 times and impregnate 1 ml of the prepared ammonia into each filter paper, and put it into 5 500 ml polycontainers, and again add paper deodorant with filter paper (A)-(d). In combination or alone or in half or one quarter, four poly containers were sealed, and then all five poly containers were sealed to change the odor after standing for a predetermined time.

The results are shown in Table 4. From the results in Table 4, it can be seen that the paper-like deodorant of the present invention exhibits a very good deodorizing action against the ammonia odor.

[Table 4]

Example 8

(A). Preparation of Lead Maintenance

27.5 g of ferrous sulfate sulfate (molecular weight 278.03) was dissolved in water to make 100 ml, and 0.5 g of L-ascorbic acid was added to dissolve to prepare an aqueous solution of ferrous L-ascorbic acid solution. Next, this stock solution was diluted 50 times with water to prepare a fresh oil retainer.

(B). Leading Maintenance Test

Spinach (100 g) and banana (1 115 g) pork (100 g) just purchased from the market were sprayed with 5 ml each of the freshness oils, and the polyethylene transparent bag (30 cm × 25) was stored at room temperature (20 ° C.). Sealed and preserved in cm), the change in the freshness of each food and the occurrence of decay (sludge of liquid, rotting odor) were observed. The test in the absence of treatment was performed in parallel, and the results are shown in Table 5 below.

Using the freshness retainer of the present invention compared to the comparative example from the results of Table 5, freshness could be maintained for 4-5 days in spinach, and in the case of bananas, the yellow color of the peel returns to the original green color, It can be seen that the grains of the worms are held firm for 5-6 days longer than the comparison. In pork, it also lasted for three to four days.

In addition, the result of test by spraying the aqueous solution of L-ascorbic acid (10% by weight) to spinach, banana and pork in the same manner as described above was almost the same as the comparative example of Table 5, the effect of freshness was not seen.

[Table 5]

Example 9

(A). Preparation of antiseptic preservatives impregnated with L-ascorbate

27.5 g of ferrous sulfate sulfate (molecular weight 278.03) was dissolved in water to make 100 ml, and 0.5 g of L-ascorbic acid was added to dissolve to prepare an aqueous solution of ferrous L-ascorbic acid solution. Granules of activated carbon (combined with 20 parts by weight of commercially available powder activated carbon, 20 parts by weight of zeolite, and 60 parts by weight of bentite are formed by extruding, drying, and manufactured by a conventional method, granule diameter 1.5-2.5 mm). 15 wt% of the aqueous solution of ferric L-ascorbate prepared above was impregnated, and dried at room temperature for 24 hours after impregnation to prepare a granular fresh oil retainer.

(B). Leading Maintenance Test

Granules prepared in (A), each containing three transparent polyethylene bags (approx. 30 cm x 25 cm), each containing spinach (100 g), banana (110 g) and pork (100 g), which have just been purchased from the market. 5 g of each freshener was added to each bag, and the doorway of the bag was sealed.

After doing so, it was stored at room temperature (about 20 ° C.) to test the change in freshness of each food and the state of decay (smooth liquid generation, decay smell).

In addition, the same test was done similarly to the above except that the said granular freshness retainer was not put in the bag for comparison. These results are the same as in Table 6, and from the results in Table 6, it can be seen that the freshness retaining agent of the present invention exhibits an excellent freshness retention effect in any of spinach, banana and pork.

[Table 6]

Example 10

(A) Preparation of Sludge

27.5 g of ferrous sulfate hexahydrate (molecular weight 278.03) was dissolved in water to make 100 ml, and 0.5 g of L-ascorbic acid was added thereto to dissolve to prepare an aqueous solution of ferrous L-ascorbic acid solution. This stock solution was diluted 300-fold with water, and a diluent of about 1-2 cm in size was prepared.

(B) Freshness maintenance test of fish and shellfish

In a box of foamed styrol (50 cm long x 30 cm wide x 30 cm deep), the above-mentioned ice cream material was placed in a thickness of about 10 cm. The lid was then closed and preserved for 5 days. The temperature in a box was 3 degrees C or less. For comparison, fish and shellfish were stored in a foamed styrol box for 5 days in the same manner as above using a normal fish. The fish were divided into two fresh ones just purchased from the market and served in two tests under the same conditions. After 5 days, the lid was opened and 10 monitor members evaluated the freshness of both fishes by comparing their appearance, body rigidity, eating feeling, and taste. The summary of the results is shown in Table 7.

[Table 7]

According to the results of the above table, although the shelf life is winter, although the freshness was greatly reduced in the test of the use of ordinary ice, according to the present invention, there was no fishy smell to prevent it, and the reaction felt when light or chewed. As a favorable state, it turns out that the freshness of a fish can be maintained for a long time.

Claims (4)

It includes divalent ions and L-ascorbic acid, and the divalent ions are present at a concentration of at least 0.15% by weight in aqueous solution, and L-ascorbic acid is converted to metal iron. A chemically active aqueous solution, characterized in that it is present in a ratio of 2.0 parts by weight or more with respect to 100 parts by weight of the ferric ion. A chemically active solid, comprising divalent ions and L-ascorbic acid, wherein L-ascorbic acid is present in an amount of 2.0 parts by weight or more based on 100 parts by weight of ferric ions expressed in terms of metal iron. Substance of state. The drug according to claim 1, which is selected from deodorants, fungicides, freshness oils and water treatment agents used as aqueous solutions. The drug according to claim 2, which is selected from deodorants, fungicides, freshness oils and water treatment agents which are solid substances.

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