CA1298954C - Compound containing ferric ferrous salt and a producing method thereof - Google Patents

Abstract

Abstract A stabilized mixture containing ferric ferrous salt and a producing method thereof are provided in the present invention. Said mixture comprises ferric ferrous salt and a salt of alkali metals or a compound containing a metal which belongs to zinc family, and said producing method of said mixture comprises adding ferric ferrous salt into an aqueous solution of strong acid and then adding a salt of alkali metals or a compound containing a metal which belongs to zinc family. Said mixture containing ferric ferrous salt may be very useful in a wide variety of fields, such as water cleaning, keeping freshness of vegetation, antisepsis, antifungi, antibacteria, rust preventing, effluent treatment, soil improvement, ionization control, feed enriching, petroleum improvement, antistatic technique, and the like.

Description

A COMPOUND CONTAINING FERRIC FERROUS SALT
AND A PRODUCING METHOD THEREOF

BACKGROUND OF THE INVENTION
Field of the Invention 5The present invention relates to a new stabilized mixture containing ferric ferrous salt and a new producing method thereof. More particularly the present invention relates to a new mixture comprising ferric ferrous salt and a salt of alkali metals or a compound containing a metal which belongs to zinc family. Furthermore, the invention relates to a new producing method of said mixture comprising adding ferric ferrous salt into an aqueous solution of strong acid and then adding a salt of alkali metals or a compound containing a metal which belongs to zinc family.
15In a preferred embodiment there is provided a stabilized mixture comprising the ferric ferrous salt Fe2Cls together with at least one of NaCl and ZnCl2.
Description of the Prior Art Hitherto, ferric ferrous salt such as ferric ferrous chloride has been known and ferric ferrous salt is known as complex of ferric salt and ferrous salt. The chemical formula of said ferric ferrous chloride may be as follows:

nFeC12.mFeC13.XH20 Common ferric ferrous chlorides are 2FeCl2.FeCl3.xH2O and FeCl2.2FeCl3.xH2O and said compound is known to have adsorption ability. Nevertheless, ferric ferrous salt is unstable, and so no usefulness of said ferric ferrous salt has been found out yet.

SUMMARY OF THE INVENTION

Accordingly, an object of the present invention is to provide a mixture in which ferric ferrous salt is stabilized.
Another object of the present invention is to utilize the special character of said stabilized ferric ferrous salt in a wide variety of fields.
Further object of the present invention is to provide a producing method of said mixture containing ferric ferrous salt.
Briefly, these objects of the present invention can be attained by a new mixture which comprises ferric ferrous salt and a salt of alkali metals or a compound containing a metal which belongs to zinc family and a new producing method of said mixture comprises adding ferric ferrous salt into an aqueous solution of strong acid and then adding a salt of alkali metals or a compound containing a metal which belongs to zinc family.

DETAILED DESCRIPTION

Ferric ferrous salt of the instant invention may be prepared by the following method:
2FeC12.FeC13.xH20 NH4[Fe2llFelll(CO3)3O]2H2O is dissolved in a small amount of the concentrated hydrochloric acid aqueous solution and the - . ~
~, ~B9~;4 resulting solution is carefully evaporated while preventing contact of air.
FeCl2.2FeC13.xH2O
KOH is added into a concentrated aqueous solution of ferric chloride and fexrous chloride at the boiling point and the resulting hydroxide is settled. Said hydroxide is separated and dissolved into HCl aqueous solution and the resulting solution is evaporated on calcium oxide and concentrated sulfuric acid.

FeC12.FeC15.xH20 1. From Ferric chloride Ferric chloride is dissolved into aqueous solution of sodium hydroxide and then said solution is neutralized by hydrochloride aqueous solution. The resulting neutralized solution is evaporated to obtain crystal. Said crystal is collected and dissolved into isopropanol-water mixture. The resulting solution is filtered and then concentrated to obtain Fe2Cls.xH20.

2. From Ferrous sulfate Ferrous sulfate is dissolved into HCl aqueous solution and then the resulting solution is concentrated to obtain crystal. Said crystal is collected and dissolved into isopropanol-water mixture. The resulting solution is filtered and then concentrated to obtain Fe2O5.xHzO.
For preparation of the mixture of the present invention by using said ferric ferrous salt, a salt of alkali metals or ~298954 a compound containing a metal which belongs to zinc family is added into aqueous solution of said ferric ferrous salt. Salt of alkali metals in the present invention may be such as KCl, NaCl~ LiCl~ K2SO4, Na2SO4, Li2So4, CH3COOK, CH3COONa, CH3COOLi and the like, and a compound containing a metal which belongs to zinc family in the present invention may be such as ZnCl2, CdCl2, ZnSO4, CdSO4, (CH3COO)2Zn, (CH3COO)2Cd, ZnO~ CdO~ Zn(OH)2, Cd(OH)2 and the like.
Further, a desirable producing method of said mixture of the present invention is a one-step method wherein ferric ferrous salt is produced under the existence of salt of alkali metals or a compound containing a metal which belongs to zinc family.
One of desirable one-step methods is as follows:
Ferrous sulfate is dissolved into HCl aqueous solution and further, sodium chloride or a compound containing a metal which belongs to zinc family is dissolved into said solution.
The resulting solution is concentrated to obtain crystal.
Said crystal is collected and dissolved into methanol and the resulting solution is filtered and then concentrated to obtain the stabilized mixture of the present invention. The resulting mixture of the present invention is purified by washing with pyridine, and then recrystallized by ethanol.
The mixture of the present invention is used singly or as a complex with other materials in a wide variety of fields, such as water cleaning, keeping freshness of vegetation, , . ~

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antisepsis, antifungi, antibacteria, rust preventing, effluent treatment, soil improvement, ionization control, feed enriching, petroleum improvement, antistatic technique, and the like. In said complex of the mixture of the present invention, other material, such as aluminum, sodium chloride, vegetable fiber, protein is added to the mixture comprising ferric ferrous salt and a salt of alkali metals. Said material to be added should be selected according to purposes of use of the mixture of the present invention.
Further, it becomes clear that metals treated by the mixture of the present invention possess amplified and/or altered special character of the mixture of the present invention. Said metals to be treated by the mixture of the present invention may be such as Fe, Cu, Al, and the like.
For said treatment, powder, flakes, particles, strip, and the like of said metal is soaked into an aqueous solution of the mixture of the present invention, and then said metal is separated from said solution. In said treatment, existence of carbon, silica compound, such as silicate, silicon oxide, and the like, or material containing silica such as zeolite, sand, and the like increases and/or alters the effect of the treatment.

Example 1 (Preparation of Fe2Cls-NaCl compound) one gram of ferrous sulfate (FeSO4.6H2O) was put into 5 ml of 12 N HCl aqueous solution and after sufficlent ( agitation insoluble materlals in said solution were removed by filtration using filter paper (No. 5C). Sodium chloride (0.1 g) was added into said filtered solution and said solution was concentrated in vacuum. The result-ing residue was collected and dissolved into 10 ml of methanol and said methanol solution was drled in a desiccator. The resulting dried material was washed with a small amount of pyridine and then crystallized in 10 ml of ethylalcohol. 10.6 mg of Fe2C15-NaCl compound was obtained in the form of fine crystal.

Example 2 (Preparation of the original solution A) 10.6 mg of Fe2C15-NaCl compound prepared by Example 1 was dissolved lnto 1 liter of water and further, 10 8 Of ferric chloride (FeC13-6H20) was added into said solution. To obtain the or.lglnal solution, the resulting solution was diluted by water (1000 X).

Example 3 (Preparation of aluminium complex) 0.5 ml of concentrated HCl aqueous solution was 2~ added into 500 ml of the original solution A obtained in Example 2 and aluminium powder was added lnto the resulting solution. After sufficient agitation, said solution with dispersed said aluminium powder was kept for 24 hours and then said treated aluminium powder was separated from the solution. Said separated aluminium powder was further put into the original solution A in which 0.5 g of caustic 'Ai ~ ~298954 soda and 0.5 g of glucose were added and after sufflcient agitation, said solution with dispersed said alumlnium powder was kept for 24 hours. Said treated aluminium powder was separated from the solution and dried to obtain the complex A-l.

Example 4 (Preparation of sodium chloride complex) 5 g of t-he complex A-l and lO g of glucose was added into lO liter~ of sea water and said treated sea _ water was kept for more than 5 days. Said treated sea water was filtered by uslng fllter paper (No. 5C) and 2 litersofsaid filtered sea water was put into an enameled vessel. 500 g of sodium chloride was added into said treated sea water in the enameled vessel and dissolved completely by heatlng at 50C and further, l mg of the complex A-l was added. The resulting solution was evaporated by heating until the volume of said solution decreased to 200 ml and crystallized sodium chloride complex (the complex A-2) was obtained during said evapora-tion. The resulting complex A-2 was dried in a vacuum dryer.

ExamPle 5 (Preparation of magnesium chloride complex) After the complex A-2 was collected in Example 4, the remaining solution was further concentrated on the water bath until the volume of said solution decreased to 20 ml and crystallized materlals were removed from said concentrated solution. Magnesium chloride (MgCl2-6H20) 129~954 was added into the remainlng solution to make a saturated f solution of magnesium chlorlde. Sald saturated solution was used as magnesium chloride complex (the complex A-3~.

Example 6 (Preparation of vegetable fiber complex) 100 g of material containing a large amount of vegetable fiber, such as beet pulp, droppings of Herbivora, and the like was suspended ln 1 liter of water and then 1 g of the complex A-l was added. After sufficient agitation, said mixture was kept overnight and then heated at a temperature below 100C to dry. The vegetable fiber complex (the complex A-4) was finally obtained in the form of the dried powder.

ExamDle 7 (Preparation of soybean-protein complex) 100 g of soybean-protein was suspended ln 1 liter of water and then 1 g of tne complex A-l was added.
After sufficient agitatlon, said mixture was kept overnight and then heated at a temperature below 100C to dry.
The soybean-proteln complex (the complex A-5) was finally obtai~ed in the form of the dried powder.

2~ Example 8 (Use of the complex A-l) 100 g of the complex A-l was put in a bag of nylon cloth and said bag containing the complex A-~ was suspended in water in a concrete tank of which capacity was 20 tons. In spite that said water to be treated had high concentration of iron and silicate, no duck weeds ',A~

propagated in said water during the treatment and said treated water stayed clear and fresh from May to August.
Further, no rust and scales were found on the surface of the metal pipe ln said tank.

Example 9 (Use of the complex A-2) The cut ends by the root of greens such as Chinese cabbage, lettuce, splnach, and the llke were soaked in 1 ppm aqueous solutlon of the complex A-2 for 30 min and after soaking, said soaked parts of greens were respectively covered with vlnyl chloride films. Said treated greens stayed fresh for one week at room temperature while untreated greens withered wlthin 3 days.

Example 10 (Use of the complex A-3, No. 1) The origlnal solution was prepared by dllutlng the complex A-3 first wlth distilled water at 108 X and then with sea water at 100 X. Sald origlnal solution was added lnto emuision of cutting oil at 1/1000 ln volume and said treated emulsion was kept at 30C. No mlcro-organlsms propagated ln the emulslon and the emulsion did not denature for more than 35 days whlle many mlcroorganisms propagated in the untreated controlled emulslon and said untreated emulsion completely coagulated after 5 days.

Example 11 (Use of the complex A-3, No. 2) The orlginal solutlon of Example 10 was dlluted 12~1~954 . ~

with distilled water at 1000 X and the sawdust, aluminium flake, and sea sand were respectively soaked in said diluted solution for 24 hours. Said treated sawdust, aluminium flake, and sea sand were respectively separated from said solution and dried. 50 g of mixture of the treated sawdust and the treated aluminium flake (50:1 weight ratio) were put into a glass column (diameter 3.5 cm) and effluent (BOD 9100 mg/liter) from a sugar refining factory was put through said glass column at the rate of 50 ml/minute. Further, said effluent was put through a glass column (diameter 3.5 cm) at the rate of 50 ml/minute in which 100 g of mixture of the treated sea sand and the treated aluminium flake(100:1 weight ratio) was put BOD of the treated effluent decreased to 14 mg/liter.

Example 12 (Use of the complex A-3, No. 3) 8 liters of sea water was put into a plastic vessel and 1 g of the treated sawdust of Example 11 was added to said sea water. A graphite plate (19.5 X 10 cm) as an anode and a copper plate (19.5 X 10 cm) as a cathode were respectively inserted into said treated sea water.
The distance between anode and cathode was 35 cm and 0.2 volt direct current was charged to said electrodes while air was blown into said sea water while charging the direct current. Immediately a large amount of white clots and brown clots were formed around and/or on the cathode and a metal film was formed on the surface of the sea water. After charging the direct current for 48 hours, no chlorine ion was detected in said sea water.

Example 13 (Use of the complex A-3, No. 4) Rice plants were cultivated by using only the treated sea water of Example 12 and no nulsance to growth of the rice plants was recognized.

Example 14 (Use of the complex A-4) 300 g of the complex A-4 was mlxed lnto soil of 10 a of the nursery and seedllngs of rice plant were cultivated in said nursery by using the ordinal method.
Said seedlings were replanted to a rice field and excellent growth of said seedlings was recognized without the lneffectual stem ~orklng. 793 kg of rice was harvested per 10 a of said rice fleld while only 480 to 510 kg of rice was harvested per 10 a of the untreated controlled rice fleld.
Example 15 (Use of the complex A-5) 0.1% of the complex A-5 was mixed with the feed and said feed was adminlstered to a cow with no appetlte. The appetite of sald cow lncreased very much 2~ and said cow recovered from the mastitis-like condition, and two to three days after administering of the feed, said cow's mllk production lncreased by about 10%.

Example 16 (Treatment of fllter) (1) Preparation of treating solutlons I 5 g of ferrlc chlorlde (FeC13-6H20) was added into 50 ml of the orlginal solutlon A and further, the solutlon wherel~ 23 g of caustlc soda was dlssolved ln 50 ml of water was added into said solution. The dlstllled water was added lnto the resulting solutlon to increase the solution to the total amount of 200 ml. Thus, the first solution was prepared.

II 5 g of ferrlc chlorlde (FeC13-6H20) was added into 50 ml of the orlginal solutlon A and further, 50 ml of the concentrated HCl aqueous solutlon was added into sald solutlon to lncrease the solution to the total amount of 100 ml. Thus, the second solution was prepared.

III The complex A-3 was diluted by the distllled water at 108 X and further, the resulting diluted solution was diluted by sea water at 100 X.
Thus the third solutlon was prepared.

(2) Treatment of filter Three vessels containing respectively 10 liters of distilled water were prepared, and 10 ml of said treating solution was added into each vessel to prepare the first treating solution, the second treating solution, and the third treating solution. A filter was soaked in the first treating solution for 3 hours; second treating solution for 3 hours; and the thlrd treating solution, more than 10 hours. Thus the treated fllter was obtained.

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Example 17 (Use of the treated filter) Subterranean water containing a large amount of iron component was filtered by using the treated filter of Example 16 and radishes were water-cultured by using said treated water. As the result, the rate of growth of said radishes increased, and decaying by microorganisms was completely prevented and high graded radishes were obtained. The radishes cultured by untreated water somewhat decayed and its growth was slow.

Example 18 (Treatment of plastic film) (1) Preparation of the treating solution The complex A-3 was diluted by the distilled water to 108 X and further, said solution was diluted by sea water to 100 X. Five ml of the resulting solution, 5 g of citric acid, and lO g of the complex A-5 were added to 4995 ml of distilled water and after sufficient agitation, an iron piece (5 X 7 cm) wherein 0.5 ml of acetic acid salt of ~-tocopherol was applied respectively on both surfaces of said iron piece was immersed in the resulting solution and kept overnight at room temperature.
Then, said iron piece was removed from the solution and said solution was vacuum-filtered by the filter paper (No. 5C). The resulting filtered solution was used as the treating solution.

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~2~954 (2) Treatment of plastic film ( The treating solution was applied on the surface of the film of polyvlnyl chloride and the resulting film was dried.
The freshness test of fruit and vegetable by using said treated film was carried out as follows:
Bananas were wrapped with said treated film and kept at 30C. Said wrapped bananas stayed fresh for three days while bananas wrapped wlth the untreated controlled fllm turned black ln the most parts of the peellngs and some eatable parts of bananas decayed in one day.
Splnach and leeks were respectively wrapped with said treated film and no colour change of spinach and leeks were recognized and they stayed fresh after three days, while splnach and leeks wrapped wlth the untreated controlled film remarkably withered.

ExamPle 19 (Preparation of ferric ferrous chloride-ZnC12 compound) 1 gra~ of ferrous sulfate (FeS04 6H20) was put into 5 ml of 12 N HCl aqueous solution and after sufficient agitation, insoluble materials in said solution was removed by filtration using filter paper (No. 5C). 0.1 g of zinc chloride was added into said filtered solution and said solution was concentrated in vacuum. The resulting residue was collected and dissolved into 10 ml of methanol and said ~ethanol solution was dried ln a desiccator. The resulting dried material was washed with a small amount of pyridine, and then crystallized in 10 ml of ethylalcohol 15.2 mg of ferric ferrous chloride-ZnCl2 compound was obtained in the form of fine crystal.

Example 20 (Preparation of the original solution B) One gram of ferric ferrous chloride-ZnCl2 compound in Example 19 was dissolved into 50 ml of the distilled water, and further, 4 g of ferric chloride (FeCl3.6H2O) was added into said solution. To obtain the original solution B, the concentrated HCl aqueous solution was added to the resulting solution to increase the solution to the total amount of 100 ml.

Example 21 (Recovering of isolation oil) Copper piece (5 X 10 cm) was immersed in the diluted original solution B (106 X), and said copper piece was taken out from said solution after immersing for 24 hours.
Said treated copper plate was inserted into denatured isolation oil and kept for 10 days at room temperature. After said treatment, said copper piece was taken out from the isolation oil and the electric breakdown endurance of said treated isolation oil was determined for four samples. The result is shown in Table 1. The numbers in Table 1 show the electric breakdown endurance of the isolation oil (K.V).

~ - 1298954 Sample No. 1 2 3 4 average _ Treated oil50~ 50<50~ 50~ 50<

(control)30 2 a32 27 29.3 Table 1 Referring to Table 1, it may be clear that said isolation oil was recovered to the same quality as fresh oll.

Example 22 (Antistatic agent of textile) A polyester cloth (100 cm ) was soaked in the diluted original solution B (106 X) and kept for 24 hours. After treating for 24 hours, said polyester cloth was taken out from said solution and dried. The frictional charge voltage and its half-valved period about said treated polyester cloth were determined. The results are shown in Table 2.

Frictional chargeHalf-valved Sample voltage (V) period _ . .

Treated cloth24 4.0 . . .
Untreated cloth 7800 more than 180 Table 2 Example 23 (Improvement of crude petroleum) An iron piece (5 X 10 cm) was immersed in the diluted original solution B (106 X), and said iron piece was taken out from said solution after immersing for 24 hours. Said treated iron piece was inserted into crude petroleum and kept for 2 hours at room temperature. After said treatment, said iron piece was taken out from the crude petroleum and the combustion test of said treated crude petroleum was carried out. As the result, less oil soot was produced and better igniting effectiveness was obtained comparing with untreated crude petroleum. The results of the analysis of the treated crude petroleum are shown in Table 3.

¦Water content (by XF method) 172 ppm Ash content 0.01% >
Carbon residue 0.23%
Sulfur content 0.03%
Nitrogen content 0.08%
Specific gravity (15/4C) 0.7805 API degree (60F) 49.72 Kinematic viscosity (30C) 1.193 Cst Flash point (TAG) -39.0C
Flow temperature -42.5C

Heating valve 11050 cal/g Table 3 Example 24 (Improvement of lubricating oil) An iron ring was immersed in the diluted original solution B (106 X) and said iron ring was taken out from said solution after immersing for 24 hours. The following friction test was carried out:
The surfaces of a pair of T.P. soft steel plate were respectively contacted with the upper and lower parts of a shaft rotating at 373 rpm while loading the weight of 6.5 kg with supplying said treated lubricating oil to the contacting surfaces. After contacting with said loading for 8 hours, the valve of (Reduced thickness~ X (length of contacting part~ of said T.P soft steel plate which contacted with the upper part of said shaft was 14 X 10 2 Lmm)2 and while said valve of the untreated controlled lubrication oil was 30 X lo~2~mm~2 Example 25 (Effluent treatment) 3 kg of iron scraps were immersed in 5 liters of the diluted original solut~on B (10 X) and sald lron scraps were taken out from said solution after immersing for 48 hours. Said iron scraps were put on the coarse sand layer (thickness 10 cm, sectlonal area 2.3 m ) in a column. Said three columns were combined in series and effluent containing raw sewage, effluent from kitchens and the like was continuously put through said three columns at the rate of 1 ton per day. After treating for 3 days, treated effluent became clear and the treatment of said effluent was proven to be satisfactory.

The quality of the treated effluent after treating for 5 days is shown in Table 4.

~2989S4 ¦ QualityBefore treatment After treatment ¦BOD (mg/liter)8480 2.0 COD (mg/liter)1360 0.5 SS (mg/liter) 56 0 Extract with 488 0.3 n-hexan (mg/liter) The number of4.3 X 106 0 E. coli~cm3 Phosphoric ion5.2 0.1 (mg/liter) ._ Table 4 Example 26 (Antisepsis and antifungi) 0.1 g of iron powder and 1 ml of soy sauce were added into 25 ml of the diluted original solution B (106X) and after sufficient agitation, said mixture was kept overnight. Then, said mixture was filtered through the filter paper (No. 5C) and 1 ml of said filtrate was added into 1 liter of soy sauce diluted 2 X
with water and said mixture was continuously agitated by the magnetic stirrer at room temperature.
After agitating for 3 weeks, no propagation of fungi or bacteria was recognized in the treated soy sauce and the flavour of the treated soy sauce also did not change, while remarkable propagation of fungi and bacteria and putrefaction were recognized in the untreated controlled soy sauce.
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Exampie 27 (Rust preventing) 0.1 g of iron powder and 0.1 g of carbon powder were added in~o the diluted original solution B (10 X), and after 24 hours, said mixture was filtered through filter paper (No. 5C). An iron piece (5 X 10 cm) gathering rust was immersed in 150 ml of said filtrate for 24 hours.

For the evaluation for rust preventing, said treated iron piece was immersed in sea water for 30 days. The surface of said treated iron piece became dark and no increase of () rust was recognized, while a remarkable increase of rust was recognized on the surface of the untreated controlled iron piece.

Example 28 (Deodorizing) Four impingers were connected in series and 350 ml of the diluted original solution B (10 X) was respectively put in the first, second, third impingers and 150 ml of the diluted original solution B was put in the fourth impinger.
The distance between foaming plate of the impinger and surface of the solution was respectively controlled about 8 to 9 2() cm. Four types of gas to be treated were respectively put through said four impingers and smell concentration for each treated gas was determined. Smell concentration is defined as magnification of diluting when no smell of the treated gas is detected while diluted with air. The results are shown in Table 5.

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Treating time (min) gas A gas B gas C gas D

Untreated 5000 5000 5000020000 3 100~ 173 2000 100~
100> 214 2500 100>
100~ 424 2500 100>

Table 5 Gas A: Exhaust gas from the mixing process of raw rubber.
Gas B: Exhaust gas from the boiling process of materials of beer. ~ Gas C: Exhaust gas from the boiling process of materials of beer.
Gas D: Exhaust gas from the fermenting process of yeast.

Referring to Table 5, it may be clear that the com-pound of the present invention has a remarkable and durable deodorizing effectiveness.

Claims (5)

1. A stabilized mixture comprising the ferric ferrous salt Fe2Cl5 together with at least one of NaCl and ZnCl2.

2. A mixture according to claim 1 in the form of an aqueous solution.

3. A process for producing a mixture according to claim 1 comprising dissolving FeCl5 into an aqueous solution of HCl and then adding NaCl or ZnCl2.

4. A process according to claim 3 comprising dissolving ferrous sulfate into aqueous solution of hydrochloric acid, further, dissolving sodium chloride or zinc chloride into said solution, concentrating the resulting solution to obtain crystals, collecting and dissolving said crystals into methanol, filtering the resulting solution, and concentrating said filtrate.

5. A process according to claim 4, wherein the resulting filtrate is further washed with pyridine and then recrystallized by ethanol.