JPH0613408B2 - Method of manufacturing active formulations - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to antibacterial, antifungal, wastewater treatment, petroleum reforming and fiber,
The present invention relates to a method for producing an active composition having a high degree of utility in a wide range of applications such as antistatic agents for plastic products, the active composition comprising an active substance presumed to be a divalent and trivalent iron salt, It consists of a zinc compound.

Known divalent and trivalent iron salts are, for example, Fe ₃ Cl ₇ .xH ₂
O or Fe ₃ Cl ₈ · xH ₂ O and the like are present, but these divalent and trivalent iron salts are considered to be complex salts of divalent iron and trivalent iron. Further, these divalent and trivalent iron salts have so far been found to have an adsorbing action based on divalent iron, and have not been recognized to be particularly useful.

However, the present inventors have discovered the surprising fact that these divalent and trivalent iron salts have extremely interesting actions such as biologically active action and ionization-inhibiting action, and such action is particularly novel. It was confirmed that it is remarkable in the active substance presumed to be Fe ₂ Cl ₅ which is an iron salt, and that when this active substance is mixed with a zinc compound, the active substance is stabilized and its action becomes more remarkable, The present invention has been completed.

The present invention is described in detail below.

The active substance of the present invention appears to be a complex rather than a mere 1: 1 equivalent mixture of FeCl ₂ and FeCl ₃ , prepared from ferric chloride by the following process.

Ferric chloride is dissolved in an aqueous caustic soda solution, neutralized with hydrochloric acid, concentrated, and the obtained crystals are dissolved in an isopropanol-water mixed solution, and the solution is concentrated after excess to obtain crystals of the active substance.

The zinc compound used in the present invention means ZnCl ₂ , Zn
Compounds such as salts of inorganic or organic acids of zinc such as SO ₄ , (CH ₃ COO) ₂ Zn, ZnO and Zn (OH) ₂ , hydroxides and oxides.

A more desirable method of obtaining the active formulation of the present invention is to allow the zinc compound to be present in the production of the active substance instead of once preparing the active substance and then preparing the formulation as in the above method. It is a method of obtaining the active composition of the present invention in one step. An example of such a method is shown below.

After dissolving ferric chloride in a caustic soda aqueous solution, further dissolving zinc chloride in the solution, neutralizing the mixture with hydrochloric acid, and concentrating, the resulting crystals are dissolved in methanol, and the solution is concentrated after excessively An active formulation is obtained. The active formulation according to the invention obtained by the above process is further purified by washing with pyridine and recrystallisation with ethanol.

The active formulations according to the invention are used in a wide variety of applications such as those mentioned above, either alone or as a complex. In the case of a complex, the active formulation according to the invention is additionally provided with an adduct.
A wide range of substances such as metals, vegetable fibers, and chemical products are applied as the above-mentioned additive, and the above-mentioned additive is appropriately selected according to each application.

Furthermore, it has been found in the present invention that the metal treated with the active formulation of the invention retains the action of the active formulation of the invention in a further amplified or modified state. Metals treated with the active formulations of the present invention include iron, copper, aluminum and the like. To treat the metal with the active formulation of the present invention, powdery, granular, ribbon-like strips of the metal are soaked in the active formulation of the present invention and then the metal is separated from the aqueous solution. In the treatment, carbon or a silicon compound such as silicate or silicon oxide,
Alternatively, the presence of a silicon-containing substance such as zeolite or river sand enhances the treatment effect.

Examples for more specifically explaining the present invention will be described below.

Example 1 (Production of zinc chloride-containing ferrous chloride-ferric chloride) 1 g of ferric chloride was put in 5 ml of 10N caustic soda aqueous solution, stirred and neutralized with 10N hydrochloric acid aqueous solution, and then insoluble components were removed from the paper. (No. 5C) A part of the solution portion is sampled, concentrated under reduced pressure, and dried in a desiccator. 10 ml of an 80% by weight aqueous solution of isopropanol was added to the obtained dry powder, and the eluted components were collected and concentrated under reduced pressure to remove the solvent and dry. Crystals of the active substance are obtained by repeating the above extraction-concentration-drying operation several times.

A 5% by weight aqueous solution of the crystals was prepared, and 0.01 ml thereof was used as a paper chromatograph paper No. 51A (2 cm × 40 cm).
c) Spot 3 cm inside from the lower end, and perform upward development at 20 ° C. for 15 hours using a mixture of n-butanol: acetic acid: water = 5: 1: 4 by volume as a developing solvent. After the development, the paper was dried and then spray-developed on the paper with a 1% by weight aqueous solution of potassium ferricyanide as a coloring reagent, and it was confirmed that the developed position of the crystal was Rf = 0.07 at one spot.

Then a similar paper chromatograph test was performed with FeCl
_When carried out on a 1: 1 equivalent mixture of ₂ and FeCl ₃ , the development result is 2 spots, Rf = 0.095
It was confirmed that (FeCl ₂ ) and Rf = 0.36 (FeCl ₃ ).

The above paper chromatographic test confirmed that the crystal was not a mixture but a single compound.

Next, 0.1 g of the crystal is dissolved in distilled water to make 100 ml, and a test solution is prepared. 2.5 ml of the solution is placed in a 50 ml volumetric flask, and 2.5 ml of 0.1 wt% orthophenanthroline aqueous solution and sodium acetate-acetate buffer solution (pH
4.5) Add 2.5 ml and fill up to the marked line with distilled water. Three
After standing at room temperature for 0 minutes, the absorbance is measured at 510 nm.
The divalent iron in the test solution was calculated from the standard curve obtained by the same method for the FeCl ₂ aqueous solution, and found to be 0.019 g / 100 ml.

Next, when the test solution was added to the volumetric flask in the above operation, 1.0 ml of a 10 wt% hydroxylamine hydrochloride aqueous solution was added in advance to reduce ferric iron to ferrous iron. The amount of ferric iron obtained in this case was 0.038 / 100 ml. Therefore, the amount of trivalent iron is 0.038g / 100ml-
It was 0.019 g / 100 ml = 0.019 / 100 ml, and it was found that the crystals contained divalent iron and trivalent iron in equivalent amounts.

From the above test, it is estimated that the crystal is Fe ₂ Cl ₅ .xH ₂ O.

Zinc chloride (special grade) in the remaining sampled solution
After adding 0.1 g, concentrate under reduced pressure.

Next, 10 ml of methyl alcohol is added and the extracted portions are collected and dried in a desiccator. The dry substance is washed with a small amount of pyridine and then put into 10 ml of ethyl alcohol to obtain a zinc chloride-containing active compound in crystalline form.
(Yield: 15.2 mg).

Example 2 (Preparation of stock solutions for various treatments) Active formulation 1 containing zinc chloride prepared according to Example 1
g is dissolved in 50 ml of distilled water, 4 g of ferric chloride FeCl ₃ .6H ₂ O is added thereto, and 50 ml of concentrated hydrochloric acid is further added to bring the total amount to 100 ml.

Comparative Example 1 The active substance is obtained without adding zinc chloride in Example 1. 1 g of the crystal of the active substance was dissolved in 50 ml of distilled water, and again, ferric chloride FeCl ₃ .6H ₂ O 4 was added.
g, and then 50 ml of concentrated hydrochloric acid to bring the total amount to 100 ml to prepare a stock solution for comparison treatment.

Example 3 (regeneration of insulating oil) 300 ml of a 10 ^6- fold diluted solution of the stock solution obtained in Example 2
Five pieces of copper pieces (5 cm × 10 cm) were put therein, and after 24 hours, they were taken out, inserted into the deteriorated insulating oil 6 and placed at room temperature for 10 days. The results of measuring the dielectric breakdown voltage of the test oil after 10 days are as follows.

If it is based on the deterioration criterion, it will be processed to the new oil stage,
It has been reformed and improved. However, in the comparative group, the active substance is unstable and the effect is slightly reduced.

Example 4 (Antistatic of Fiber) 100 cm ² of polyester cloth was put into 10 ⁶ times diluted solution 1 of the stock solution obtained in Example 2, taken out after 24 hours and dried, and then frictional electrification voltage and half-life were measured. The results were as follows.

Example 5 (Crude oil reforming) Iron pieces (5 cm x 10 cm) were added to the 10 ⁶ -fold diluted solution of the treated stock solution obtained in Example 2, and after 24 hours, this was taken out and inserted into crude oil 1. As a result of conducting a combustion test on the post-treated crude oil for 2 hours, clear reforming such as generation of oily smoke and ignition situation was recognized as compared with the untreated crude oil.

The analysis results of the treated crude oil were as follows. The numbers in parentheses indicate the case where the iron pieces treated with the comparative treatment stock solution of Comparative Example 1 were used.

Water content (KF method) 172ppm (172ppm), ash content 0.01
% Or less (0.01% or less), residual carbon 0.23% (0.
25%), sulfur content 0.03% (0.04%), nitrogen content 0.08% (0.10%), specific gravity (15/4 ° C) 0.7
805 (0.7805), API degree (60F) 49.7
2 (49.85), kinematic viscosity (30 ° C) 1.193Cst
(1.200Cst), flash point (TAG) -39.0 ° C
(-39.0 ° C), pour point -42.5 ° C (-42.5 ° C)
℃), calorific value 11050 Cal / g (11045 Cal /
g) Example 6 (Strengthening of lubricating oil) An iron ring was put into a 10 ^6- fold diluted solution of the stock solution for treatment obtained in Example 2, taken out after 24 hours and inserted into the lubricating oil, and the viscous friction resistance of the lubricating oil The test was conducted. The outline of the method is as follows. P. A decrease in the thickness of the piece is measured by applying a load between the pieces while bringing the mild steel pieces into contact with each other and supplying the lubricating oil. As a result of performing a rotation test for 8 hours, in the case of a load of 6.5 kg, (the reduction of thickness) of the piece on the upper surface when the processing ring was inserted ×
The value of (the length of the contact portion) is 14 × 10 ^-2 [mm] at ^{2, 30 × 10 -2 [mm} ] 2 to 16 × 10 ^-2 [mm in the case of control group lubricant not put ring ] ² (53.3%) was recognized. When a ring treated in the same manner as the comparative stock solution of Comparative Example 1 was added, the size was 16 × 10 ^-2 [mm] ² , which was slightly inferior to that of the stock solution of Example 2.

Example 7 (wastewater treatment) 3 kg of iron scraps were placed in a 10 ^6- fold diluted solution 5 of the treatment stock solution obtained in Example 2, and after 48 hours, the coarse sand layer [(thickness 10 cm) x (area 2) was taken out and pre-filled. .3 m ² )], and this was used as a processing unit. Three of the treatment units were combined in series, and gray water (including human waste water and kitchen waste water) continuously flowed into the combination unit at a rate of 1 ton per day. Three days after the start of inflow, the treated water changed to a clear liquid, and thereafter a stable purification treatment action was observed. The water quality 5 days after the start of treatment was as follows.

Example 8 (antiseptic / antifungal) 0.1 g of iron powder and 1 ml of soy sauce were added to 25 ml of a 10 ^6- fold diluted stock solution obtained in Example 2, and the mixture was allowed to stand overnight after stirring. After allowing to stand, the mixture was filtered through a filter paper (No. 5C), 1 ml of the filtrate was added to soy sauce 1 which had been diluted with water twice, and the mixture was continuously stirred with a magnetic stirrer.

When stirring was continued for 3 hours at room temperature (20 ° C to 25 ° C), soy sauce that had been diluted by 2 times with water (control group) was rotted due to violent growth of bacteria and mold, but treated soy sauce was tested. During the period, bacteria and fungi did not breed and the formation of flavor components was observed.

Example 9 (rust prevention) 200 ml of 10 ^6- fold diluted stock solution obtained in Example 2
Mix 0.1 g of iron powder and 0.1 g of carbon powder into 2
It was filtered through No. 5C filter paper for 4 hours. Iron pieces (5 cm × 10 cm) with rust attached were put into 150 ml of this filtrate and immersed for 24 hours. Next, when this treated iron piece was allowed to stand in seawater for 30 days, the surface of the iron piece was blackish and rust formation did not proceed during this period. As a control, a remarkable rust-preventing effect was observed in contrast to the case where the iron piece subjected to the same immersion in seawater caused remarkable red rust formation.

Example 10 (Deodorization) Four impingers were connected in series, and the 10 ^6- fold diluted solution of the stock solution obtained in Example 2 was filled in each of the three impingers of the preceding stage in an amount of 350 ml, and the final stage. The impinger was filled with 150 ml to form a deodorizing device. The distance from the foam plate of the impinger to the liquid surface of the diluting liquid was set to about 8 to 9 cm. The following gases to be treated were passed through the deodorizing device to measure the odor concentration. The odor concentration is the dilution ratio when the treated gas is diluted with air and no odor is felt. The results are shown in Table 1.

Table 1 shows that the formulations according to the invention show a pronounced deodorizing effect, which is lasting.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication H01B 3/18 9059-5G

Claims (1)

[Claims] 1. A crystal obtained by dissolving a ferric chloride salt in an aqueous solution of caustic soda, neutralizing it with hydrochloric acid and concentrating it to dissolve it in alcohol or an alcohol-water mixed solution, and then concentrating the solution to obtain a solution. For the production of an active formulation consisting of a defined active substance and a zinc compound