AU2016268593A1 - Method for treating cyanogen-containing wastewater - Google Patents
Method for treating cyanogen-containing wastewater Download PDFInfo
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- AU2016268593A1 AU2016268593A1 AU2016268593A AU2016268593A AU2016268593A1 AU 2016268593 A1 AU2016268593 A1 AU 2016268593A1 AU 2016268593 A AU2016268593 A AU 2016268593A AU 2016268593 A AU2016268593 A AU 2016268593A AU 2016268593 A1 AU2016268593 A1 AU 2016268593A1
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- cyanogen
- containing wastewater
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
Abstract
A method for treating cyanogen-containing wastewater, comprising adding a hypochlorite and hydrogen peroxide simultaneously or separately to cyanogen-containing wastewater, inducing decomposition of the cyanogen in the wastewater and/or formation of a water-insoluble compound with the cyanogen, and removing the cyanogen from the wastewater.
Description
DESCRIPTION TITLE OF INVENTION:
METHOD FOR TREATING CYANOGEN-CONTAINING WASTEWATER
TECHNICAL FIELD
[0001]
The present invention relates to a method for treating cyanogen-containing wastewater, which the method allows safe and inexpensive removal of cyanogen in wastewater by simple procedures while using as little chemicals as possible compared to conventional methods.
According to the present invention, cyanogen in any form in wastewater, namely in the form of persistent cyano complexes, easily decomposable cyano complexes and cyanide ions can be treated by simple procedures.
BACKGROUND ART
[0002]
Cyanogen has a strong impact on the ecosystem, and thus cyanogen-containing wastewater (hereinafter also referred to as “cyanogen wastewater”) cannot be released to nature without treatment. The level of cyanogen in wastewater is controlled by the Water Pollution Prevention Act, and thus wastewater must be detoxified by cyanogen removal treatment so as to fulfil the effluent standard (1 mg/L or less) before discharging into sewers and the like. In some areas, the standard is stricter than the standard mentioned above, which is controlled by regulation of local government.
Cyanogen is present in wastewater in three different forms, i.e., persistent cyano complexes, easily decomposable cyano complexes and cyanide ions, depending on the source of wastewater, the content of which may vary.
[0003]
Various methods for removing cyanogen from cyanogen-containing wastewater have been proposed and put into practical use. The methods have, however, advantages and drawbacks and are used according to the status of wastewater.
For example, the following methods may be mentioned: oxidative decomposition methods such as (1) an alkaline chlorination method in which cyanogen-containing wastewater is adjusted to be alkaline followed by injection of chlorine to oxidatively decompose cyanogen; (2) an ozone oxidation method in which cyanogen is oxidatively decomposed to nitrogen gas and a hydrogen carbonate salt by strong oxidative power of ozone; and (3) an electrolytic oxidation method (electrolysis method) in which cyanogen is decomposed by electric current with insoluble electrodes to perform oxidation reaction; insoluble complex methods such as (4) a Prussian blue method in which an iron-ion-feeding compound such as ferrous sulfate is added to cyanogen-containing wastewater to produce insoluble ferri/ferrocyanide which is precipitated and removed; (5) a zinc white method in which zinc chloride and a reducing agent are added and the produced insoluble complex is precipitated and removed and (6) a reduced copper method in which a copper(II) salt and a reducing agent are added and the produced insoluble complex is precipitated and removed; (7) a biological treatment method in which microorganisms (cyanogen-decomposing bacteria) conditioned to cyanogen decompose cyanogen; and hydrothermal reactions such as (8) a thermal hydrolysis method in which cyanogen-containing wastewater is maintained at high temperature to allow hydrolysis of cyanogen compounds to ammonia and formic acid and co-existing heavy metals are deposited in the form of elemental substances or oxides and (9) a wet oxidation method in which not only cyanogen is decomposed but also organic pollution materials are oxidatively decomposed.
[0004]
The present applicant has proposed the following methods for treating cyanogen-containing wastewater: (A) a method for treating cyanogen-containing wastewater by adding to cyanogen-containing wastewater a manganese compound that is soluble in hypochlorites and water and can form a manganese ion in water, and removing a produced water-insoluble manganese salt from the wastewater to remove cyanogen in wastewater (see Japanese Patent No. 4106415: Patent Document 1); and (B) a method for treating cyanogen compound-containing wastewater by conducting a first stage reaction of adding to cyanogen compound-containing wastewater formaldehyde at an amount corresponding to 1.4 times or more of the amount in moles of the contained cyanogen compound followed by a second stage reaction at pH 7.0 or higher by adding a substantially effective amount of hydrogen peroxide at 3.0 times or more of the amount in moles of the cyanogen compound (see Japanese Unexamined Patent Application Publication No. H02( 1990)-35991: Patent Document 2).
[0005]
However, the conventional methods as above require complicated steps and procedures and accordingly may need more than one reaction vessel. In addition, depending on the type of wastewater such as wastewater containing thiocyanate ion and ammonium ion, cyanogen may not be sufficiently removed, failing to comply with the effluent standard (1 mg/L or less) of the cyanogen concentration in treated wastewater, thereby leading to incapability of discharge of treated wastewater into sewers in some cases.
It is specified in the Water Pollution Prevention Act that the effluent standard of hydrogen ion concentration (pH) is 5.0 to 9.0 in the ocean area and 5.8 to 8.6 other than the ocean area. In the above conventional methods in which the pH of wastewater is adjusted to acidic or alkaline, not only the cyanogen concentration in wastewater but also the pH needs to be adjusted to be within the effluent standard by neutralization treatment before discharge into sewers.
CITATION LIST PATENT LITERATURES
[0006]
Patent Document 1: Japanese Patent No. 4106415
Patent Document 2: Japanese Unexamined Patent Application
Publication No. H02(1990)-35991
SUMMARY OF INVENTION TECHNICAL PROBLEMS
[0007]
In the method (A) disclosed in Patent Document 1, for example, the cyanogen concentration may be adjusted to be at or below the specified value by adding an excess amount of chemicals to cyanogen-containing wastewater. However, there is a need for safe cyanogen treatment by using as little chemicals as possible.
Thus, an object of the present invention is to provide a method for treating cyanogen-containing wastewater, which allows safe and inexpensive removal of cyanogen in wastewater by simple procedures while using as little chemicals as possible compared to conventional methods and which can be used regardless of the type of wastewater such as wastewater containing thiocyanate ion or ammonium ion.
SOLUTION TO PROBLEMS
[0008]
The inventors of the present invention have made intensive studies to achieve the above-described object and, as a result, surprisingly found that simultaneous or separate addition of effective amounts of a hypochlorite and hydrogen peroxide allows cyanogen in wastewater to be safely and inexpensively removed by simple procedures while using as little chemicals as possible compared to conventional methods. Thus, the inventors have completed the present invention.
[0009]
Thus, the present invention provides a method for treating cyanogen-containing wastewater, comprising adding to cyanogen-containing wastewater a hypochlorite and hydrogen peroxide, simultaneously or separately, to decompose cyanogen in the wastewater and/or produce a water-insoluble compound containing cyanogen, thereby removing cyanogen from the wastewater.
ADVANTAGEOUS EFFECTS OF INVENTION
[0010]
The present invention can provide a method for treating cyanogen-containing wastewater, which allows safe and inexpensive removal of cyanogen in wastewater by simple procedures while using as little chemicals as possible compared to conventional methods and which can be used regardless of the type of wastewater such as wastewater containing thiocyanate ion or ammonium ion.
Namely, according to the present invention, cyanogen in any form in wastewater, namely in the form of persistent cyano complexes, easily decomposable cyano complexes and cyanide ions can be treated by simple procedures while using as little chemicals as possible compared to conventional methods.
Therefore, the wastewater treated with the method of the present invention can be released to nature as it is with little impact on the environment, and the amount of water-insoluble salts (waste materials) generated after the treatment can also be reduced. Thus, the method of the present invention is industrially extremely useful.
[0011]
The method for treating cyanogen-containing wastewater of the present invention exhibits the above effect more strongly when any one of the following conditions is fulfilled. (1) the cyanogen-containing wastewater is preliminarily measured for a cyanogen content, and the hypochlorite in terms of effective chlorine concentration and hydrogen peroxide are added at 0.1 molar equivalent or more and 0.1 molar equivalent or more, respectively, relative to the measured content; (2) the cyanogen-containing wastewater originally contains one or more metal ions selected from manganese ion, iron ion and copper ion; (3) one or more metal compounds selected from a manganese compound, an iron compound and a copper compound are further added; and (4) the cyanogen-containing wastewater has pH of 9 or lower.
DESCRIPTION OF EMBODIMENTS
[0012]
The method for treating cyanogen-containing wastewater of the present invention is characterized in that cyanogen is removed from the wastewater by adding to the cyanogen-containing wastewater a hypochlorite and hydrogen peroxide, simultaneously or separately, to decompose cyanogen in the wastewater and/or produce a water-insoluble compound containing cyanogen.
[0013] ’’Decomposition of cyanogen in wastewater” and “production of a water-insoluble compound containing cyanogen in wastewater” are involved in the removal of cyanogen from cyanogen-containing wastewater according to the present invention. However, the mechanisms of the decomposition/production are not known.
The inventors of the present invention believe that “decomposition of cyanogen in wastewater” occurs as follows; hypochlorous acid and hydrogen peroxide added oxidize cyanogen and the produced cyanic acid is hydrolyzed to produce ammonium hydrogen carbonate.
The inventors of the present invention also believe that “production of a water-insoluble compound containing cyanogen in wastewater” is due to production of a water-insoluble salt of a cyanogen component and a metal ion when the wastewater contains the metal ion.
As described above and as apparent from the results in
Examples, the method for treating cyanogen-containing wastewater of the present invention is believed to allow removal of cyanogen in wastewater even with a decreased amount of chemicals compared to the conventional methods because of an effect of combined use of a hypochlorite and hydrogen peroxide and the effect of combined use of a metal ion originally in the cyanogen-containing wastewater or a metal ion further added, allowing the compounds and the metal ion to effectively act on decomposition of cyanogen and/or production of a water-insoluble compound containing cyanogen.
[0014] (Hypochlorite)
The hypochlorite used in the present invention is not particularly limited as far as the compound can produce hypochlorous acid in water. Examples thereof include alkali metal salts and alkaline earth metal salts of hypochlorous acid such as sodium hypochlorite, potassium hypochlorite, calcium hypochlorite and magnesium hypochlorite; and hydantoin derivatives. Particularly, sodium hypochlorite and potassium hypochlorite are industrially available and thus are suitably used in the present invention. The hypochlorite may be obtained by electrolysis of salt solution or marine water in an electrolysis vessel.
[0015] (Hydrogen peroxide)
The hydrogen peroxide used in the present invention may be hydrogen peroxide aqueous solutions having concentrations of 3 to 60% which are commercially available mainly for industrial use.
Hydrogen peroxide generated from hydrogen peroxide-providing compounds (also referred to as “hydrogen peroxide-generating agent”) and hydrogen peroxide generated by electrolysis of industrial water or alkaline solutions may also be used.
Examples of the hydrogen peroxide-providing compound include inorganic peracids that can release hydrogen peroxide in water such as percarbonic acid, perboric acid and peroxysulfuric acid; organic peracids such as peracetic acid; and salts thereof. Examples of the salt include sodium percarbonate, sodium perborate and the like.
The hydrogen peroxide and the hydrogen peroxide-providing compound may be used after diluting or dissolving in water so as to provide a desired hydrogen peroxide concentration upon addition.
[0016] (Addition of compounds)
According to the present invention, a hypochlorite and hydrogen peroxide are added to cyanogen-containing wastewater simultaneously or separately in order to remove cyanogen from the wastewater by causing decomposition of cyanogen in the wastewater and/or production of a water-insoluble compound containing cyanogen in the wastewater.
The hypochlorite and hydrogen peroxide may be preferably added in the form of aqueous solution, respectively. The concentration of the respective aqueous solutions may be selected by taking into account the workability upon addition thereof to cyanogen-containing wastewater or the reactivity of the compound added with cyanogen. Specifically, the concentration of the hypochlorite is about 10 to 7000 mg/L and the concentration of hydrogen peroxide is about 10 to 3500 mg/L.
[0017]
The type and concentration of cyanogen in cyanogen-containing wastewater and the type and concentration of an additional metal ion in cyanogen-containing wastewater may have an influence on the amounts of the hypochlorite and hydrogen peroxide added. Therefore, the amounts of addition may be appropriately selected according to the conditions. Specifically, cyanogen-containing wastewater prior to the treatment is measured for the cyanogen concentration and the like, and the amounts of the additives may be selected based on the measured value.
[0018]
The amounts of addition of the compounds may vary according to the cyanogen content in the cyanogen-containing wastewater to be treated as described above. However, it is preferable that the hypochlorite in terms of the effective chlorine concentration and hydrogen peroxide are at 0.1 molar equivalent or more and 0.1 molar equivalent or more, respectively, relative to the cyanogen content in the wastewater. It is more preferable that the hypochlorite in terms of the effective chlorine concentration and hydrogen peroxide are at 0.5 molar equivalent or more and 0.5 molar equivalent or more, respectively, relative to the cyanogen content in the wastewater.
When the hypochlorite in terms of the effective chlorine concentration is less than 0.1 molar equivalent, the effect of cyanogen removal may be insufficient because in some wastewater, the hypochlorite may be consumed (decomposed) by thiocyanate ion and ammonium ion in the wastewater. When hydrogen peroxide is less than 0.1 molar equivalent, the effect of cyanogen removal may be insufficient.
Examples of specific and preferable lower limit of the hypochlorite (molar equivalent) in terms of the effective chlorine concentration include 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 and 1.5.
Examples of specific and preferable lower limit of hydrogen peroxide (molar equivalent) include 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 and 1.5.
[0019] (Cyanogen-containing wastewater)
The cyanogen-containing wastewater to be treated in the present invention may be cyanogen-containing wastewater containing cyanogen compounds of metals, cyanogen ions, cyano complexes and cyano complex ions discharged from iron mills, chemical plants, metal plating plants, coke-making mills, metal surface treatment plants and the like; cyanogen-containing wastewater discharged during radiation contaminated water treatment; and cyanogen-containing wastewater discharged from soil treatment facilities. The method for treating cyanogen-containing wastewater of the present invention is particularly suitable for treatment of cyanogen-containing wastewater having a high buffering effect such as coke oven wastewater, namely cyanogen-containing wastewater containing ammonium ions.
[0020]
The cyanogen content of the cyanogen-containing wastewater to be treated in the present invention is not particularly limited; however, the cyanogen-containing wastewaters described above generally have a total cyanogen concentration of about 2 to 500 mg/L. When such cyanogen-containing wastewater is treated, the hypochlorite in terms of the effective chlorine concentration may be added to cyanogen-containing wastewater so as to be 10 to 7000 mg/L, preferably 10 to 2000 mg/L and hydrogen peroxide may be added to cyanogen- containing wastewater so as to be 10 to 3500 mg/L, preferably 10 to 1000 mg/L.
[0021]
It is preferable that cyanogen-containing wastewater originally contains one or more metal ions selected from manganese ion, iron ion and copper ion.
When cyanogen-containing wastewater originally contains the metal ion as above, the metal ion produces water-insoluble manganese salt, iron salt or copper salt by reaction with cyanogen in the wastewater, thereby promoting the effect of cyanogen removal according to the present invention.
The metal ion may have various valences according to the type of metals. In the present invention, it is preferable that the manganese ion is divalent, the iron ion is divalent and the copper ion is monovalent or divalent.
[0022]
The manganese ion concentration in the cyanogen-containing wastewater is about 0.1 to 500 mg/L.
When the manganese ion concentration is less than 0.1 mg/L, the effect of cyanogen removal may be insufficient. When the manganese ion concentration is above 500 mg/L, dissolved manganese at or higher than the effluent standard remains, which has an adverse effect on the environment and is economically unfavorable.
Examples of specific manganese ion concentration (mg/L) include 0.1, 0.5, 1.0, 2.0, 5.0, 10, 25, 50, 75, 100, 125, 150, 200, 250, 300, 350, 400, 450 and 500.
The manganese ion concentration is preferably 0.1 to 150 mg/L, more preferably 5 to 100 mg/L.
[0023]
The iron ion concentration in the cyanogen-containing wastewater is about 0.1 to 500 mg/L.
When the iron ion concentration is less than 0.1 mg/L, the effect of cyanogen removal may be insufficient. When the iron ion concentration is above 500 mg/L, dissolved iron at or higher than the effluent standard remains, which has an adverse effect on the environment and is economically unfavorable.
Examples of specific iron ion concentration (mg/L) include 0.1, 0.5, 1.0, 2.0, 5.0, 10, 25, 50, 75, 100, 125, 150, 200, 250, 300, 350, 400, 450 and 500.
The iron ion concentration is preferably 0.1 to 150 mg/L, more preferably 2 to 100 mg/L.
[0024]
The copper ion concentration in the cyanogen-containing wastewater is about 0.1 to 500 mg/L.
When the copper ion concentration is less than 0.1 mg/L, the effect of cyanogen removal may be insufficient. When the copper ion concentration is above 500 mg/L, dissolved copper at or higher than the effluent standard remains, which has an adverse effect on the environment and is economically unfavorable.
Examples of specific copper ion concentration (mg/L) include 0.1, 0.5, 1.0, 2.0, 5.0, 10, 25, 50, 75, 100, 125, 150, 200, 250, 300, 350, 400, 450 and 500.
The copper ion concentration is preferably 0.1 to 150 mg/L, more preferably 2 to 100 mg/L.
[0025] (Metal compound)
In the present invention, it is preferable that one or more metal compounds selected from a manganese compound, an iron compound and a copper compound is further added to the cyanogen-containing wastewater.
When the cyanogen-containing wastewater does not originally contain manganese ion, iron ion or copper ion, or contains the ion at a low concentration, the above effect can be obtained by adding the metal compound to the cyanogen-containing wastewater.
[0026] (Manganese compound)
The manganese compound used in the present invention is not particularly limited as far as the compound is soluble in water and can form a manganese ion in water. Examples thereof include manganese chloride, manganese sulfate, manganese nitrate, manganese acetate and the like. Among these, manganese chloride and manganese sulfate are particularly preferable in terms of the effect of removal of the cyanogen compound and manganese chloride is particularly preferred in terms of the cost for treatment of cyanogen-containing wastewater.
As used herein, “soluble in water” means that the compound has a solubility of about 1 g or more in 100 g water.
[0027] (Iron compound)
The iron compound used in the present invention is not particularly limited as far as the compound is soluble in water.
Examples thereof include compounds that can form a ferrous ion in water such as ferrous chloride, ferrous sulfate, ferrous nitrate and ferrous acetate. Among these, ferrous chloride and ferrous sulfate are particularly preferred in terms of the effect of removal of the cyanogen compound and ferrous chloride is particularly preferred in terms of the cost for treatment of cyanogen-containing wastewater.
[0028]
The method of the present invention encompasses the iron compound which is a ferrous ion-providing compound produced by adding an iron compound that can form a ferric ion in water together with a reducing agent to the cyanogen-containing wastewater or by adding an iron compound that can form a ferric ion in water to reducing cyanogen-containing wastewater to reduce in the wastewater the iron compound that can form a ferric ion in water.
Examples of the reducing agent include a sulfite, hydrazine and the like.
[0029] (Copper compound)
The copper compound used in the present invention is not particularly limited as far as the compound is soluble or dispersible in water and can form a copper ion in water. Examples thereof include cuprous compounds and cupric compounds which may be either of organic copper compounds and inorganic copper compounds.
Examples of organic copper compounds include cupric compounds such as cupric acetate, cupric benzoate, cupric citrate, copper naphthenate and cupric oleate.
[0030]
Examples of inorganic copper compounds include cuprous compounds that can form a cuprous ion in water such as cuprous chloride, cuprous fluoride, cuprous bromide, cuprous iodide, cuprous nitrate and cuprous sulfate and cupric compounds that can form a cupric ion in water such as cupric chloride, cupric fluoride, cupric bromide, cupric iodide, cupric nitrate and cupric sulfate.
Organic copper compounds may increase COD of the cyanogen-containing wastewater after the treatment. Therefore, among the above copper compounds, the inorganic copper compound is preferred, the inorganic cuprous compound is more preferred, cuprous chloride and cuprous sulfate are still more preferred and cuprous chloride is particularly preferred in terms of the effect of cyanogen removal and the cost for treatment of cyanogen-containing wastewater.
[0031]
When the cuprous compound is a cuprous salt, it is preferable to prepare a cuprous salt solution in a solvent which is hydrochloric acid, an alkali metal halide aqueous solution or ethanol because of the stability of the cuprous salt in solution.
The method of the present invention encompasses the copper compound which is a cuprous ion-providing compound produced by adding a cupric compound together with a reducing agent to the cyanogen-containing wastewater or by adding a cupric compound to reducing cyanogen-containing wastewater to reduce the cupric compound in the wastewater.
Examples of the reducing agent include a sulfite, a ferrous salt, hydrazine and the like.
[0032] (Form of addition and concentration of compounds)
The metal compound may be treated with a metal scavenger when adding the metal compound to the cyanogen-containing wastewater in order to attain a desired metal converted concentration. The metal compound may be diluted or dissolved in water such as industrial water.
Examples of the metal scavenger include liquid chelating agents.
[0033]
It is preferable that the metal compound is added in the form of aqueous solution. The concentration of the aqueous solution may be selected by taking the workability upon addition thereof to the cyanogen-containing wastewater and reactivity of the compound added with cyanogen into account. Specifically, the manganese compound in terms of the manganese ion concentration is about 0.1 to 500 mg/L, the iron compound in terms of the iron ion concentration is about 0.1 to 500 mg/L and the copper compound in terms of the copper ion concentration is about 0.1 to 500 mg/L.
When the cyanogen-containing wastewater contains manganese ion, iron ion and/or copper ion, the amounts of addition of the manganese compound, the iron compound and the copper compound may be adjusted by taking the contents of the ions into account.
[0034]
As described above, while the amount of addition of the compound may vary according to the cyanogen-containing wastewater to be treated, the concentration of the manganese compound added is, in terms of the manganese ion concentration, about 0.1 to 500 mg/L.
When the concentration of the manganese compound in terms of the manganese ion concentration is less than 0.1 mg/L, the effect of cyanogen removal may be insufficient. When the concentration of the manganese compound in terms of the manganese ion concentration is above 500 mg/L, dissolved manganese at or higher than the effluent standard remains, which has an adverse effect on the environment and is economically unfavorable.
Examples of the specific concentration of the manganese compound in terms of the manganese ion concentration (mg/L) include 0.1, 0.5, 1.0, 2.0, 5.0, 10, 25, 50, 75, 100, 125, 150, 200, 250, 300, 350, 400, 450 and 500.
The concentration of the manganese compound in terms of the manganese ion concentration is preferably 0.1 to 150 mg/L, more preferably 5 to 100 mg/L.
[0035]
As described above, while the amount of addition of the compound may vary according to the cyanogen-containing wastewater to be treated, the concentration of the iron compound added in terms of the iron ion concentration is about 0.1 to 500 mg/L.
When the concentration of the iron compound in terms of the iron ion concentration is less than 0.1 mg/L, the effect of cyanogen removal may be insufficient. When the concentration of the iron compound in terms of the iron ion concentration is above 500 mg/L, dissolved iron at or higher than the effluent standard remains, which has an adverse effect on the environment and is economically unfavorable.
Examples of the specific concentration of the iron compound in terms of the iron ion concentration (mg/L) include 0.1, 0.5, 1.0, 2.0, 5.0, 10, 25, 50, 75, 100, 125, 150, 200, 250, 300, 350, 400, 450 and 500.
The concentration of the iron compound in terms of the iron ion concentration is preferably 0.1 to 150 mg/L, more preferably 2 to 100 mg/L.
[0036]
As described above, while the amount of addition of the compound may vary according to the cyanogen-containing wastewater to be treated, the concentration of the copper compound added in terms of the copper ion concentration is about 0.1 to 500 mg/L.
When the concentration of the copper compound in terms of the copper ion concentration is less than 0.1 mg/L, the effect of cyanogen removal may be insufficient. When the concentration of the copper compound in terms of the copper ion concentration is above 500 mg/L, dissolved copper at or higher than the effluent standard remains, which has an adverse effect on the environment and is economically unfavorable.
Examples of the specific concentration of the copper compound in terms of the copper ion concentration (mg/L) include 0.1, 0.5, 1.0, 2.0, 5.0, 10, 25, 50, 75, 100, 125, 150, 200, 250, 300, 350, 400, 450 and 500.
The concentration of the copper compound in terms of the copper ion concentration is preferably 0.1 to 150mg/L, more preferably 2 to 100 mg/L.
[0037] (Order of addition of compounds)
The order of addition of the hypochlorite and hydrogen peroxide to the cyanogen-containing wastewater is not particularly limited. The compounds may be added simultaneously, or the hypochlorite and hydrogen peroxide may be added separately in this order or in the inverse order.
When the metal compound is further added, the order of addition thereof is not particularly limited. To the cyanogen-containing wastewater, the hypochlorite, hydrogen peroxide and the metal compound may be added simultaneously, or three compounds may be added separately, or two of three compounds may be added simultaneously followed by addition of the other compound.
[0038]
Namely, the order of addition includes one-stage operation, two-stage operation and three-stage operation including the following combinations. The symbol “/” means separation between operations and “(A+B)” means simultaneous addition of A and B (operation in the same step).
One-stage operation (1-1) (Hypochlorite + hydrogen peroxide) (1-2) (Hypochlorite + hydrogen peroxide + metal compound) [0039]
Two-stage operation (2 -1) (Hypochlorite) / (hydrogen peroxide) (2-2) (Hydrogen peroxide)/(hypochlorite) (2-3) (Hypochlorite + metal compound) / (hydrogen peroxide) (2-4) (Hydrogen peroxide + metal compound)/(hypochlorite) (2-5) (Hypochlorite + hydrogen peroxide) / (metal compound) (2-6) (Hypochlorite)/ (hydrogen peroxide + metal compound) (2-7) (Hydrogen peroxide) / (hypochlorite + metal compound) (2-8) (Metal compound)/(hypochlorite + hydrogen peroxide) [0040]
Three-stage operation (3-1) (Hypochlorite) / (hydrogen peroxide) / (metal compound) (3-2) (Hypochlorite)/(metal compound)/(hydrogen peroxide) (3-3) (Hydrogen peroxide)/(hypochlorite)/(metal compound) (3-4) (Hydrogen peroxide)/(metal compound)/(hypochlorite) (3-5) (Metal compound) / (hydrogen peroxide) / (hypochlorite) (3-6) (Metal compound) / (hypochlorite) / (hydrogen peroxide) [0041]
Among others, one-stage operation or two-stage operation is preferable in terms of the work efficiency.
For multiple-stage operations, it is preferable to subject the treated wastewater to sedimentation separation after every stage or after completing all operations, particularly after treatment with the metal compound. When sedimentation separation is carried out between stages, the compound of the next stage is added to the obtained supernatant. Specific examples thereof include Test Example 3.
When cyanogen wastewater having a relatively high COD (CODMn: chemical oxygen demand by acidic high-temperature permanganate method) such as 50 mg/L or higher is treated in the field by two-stage operation, it is preferable that the hypochlorite is added in the earlier stage. In view of safety, it is desirable that hydrogen peroxide is added in the later stage.
[0042] (pH of cyanogen-containing wastewater and supernatant)
The cyanogen-containing wastewater preferably has pH of 9 or lower.
When the cyanogen-containing wastewater has pH above 9, production of the water-insoluble compound may be insufficient and cyanogen may not be removed efficiently. A supernatant to which the metal compound is further added also preferably has pH of 9 or lower.
When the supernatant has pH of above 9, production of the water-insoluble compound may be similarly insufficient and cyanogen may not be removed efficiently.
The preferable lower limit of pH of the cyanogen-containing wastewater and the supernatant is about 6. However, as the cyanogen-containing wastewater to be treated generally has pH of about 6 to 9, and thus adjustment of pH is not needed.
When the cyanogen-containing wastewater and the supernatant has pH of above 9 or pH of less than 6, an acid or alkaline that does not prevent the reactions in the treatment of the present invention such as sulfuric acid or sodium hydroxide may be added to the treated wastewater.
[0043]
It is preferable that upon addition of the hypochlorite, hydrogen peroxide and the metal compound and during reaction of cyanogen with the added compounds, a mixed solution is agitated in view of the effect of cyanogen removal. It is preferable that agitation is carried out every time after a compound is added.
In order to promote reaction during agitation, it is preferable that the mixed solution is warmed up to some extent such that the added compound is not decomposed, and the temperature of the liquid is preferably about 20 to 50°C.
The time required for agitation may vary according to the amount of the cyanogen-containing wastewater, the type and concentration of cyanogen, the type and scale of the treatment device and the like; however, the time may be appropriately selected so that cyanogen and the added compound are brought into contact sufficiently. The time for agitation may generally be 10 minutes or more, more preferably 20 to 60 minutes.
[0044] (Treatment and precipitation separation)
For a series of operations including addition of compounds, mixing by agitation, sedimentation separation and removal of the water-insoluble salt, well-known devices such as an additive vessel, a reaction treatment vessel, a thickener and a clarifier may be used. Existing facilities may be converted for the purpose.
In the method for treating cyanogen-containing wastewater of the present invention, a well-known chemical such as a rust preventing agent, a corrosion inhibitor, a scale dispersing agent and a slime control agent may also be used at a range that does not inhibit the effect of the present invention.
In sedimentation separation, a surfactant or a flocculant may be added at a range that does not inhibit the effect of the present invention.
As used herein, “water-insoluble” means that a compound (salt) has a solubility of 1 g or less in 100 g water at 20°C and the compound can be separated from a liquid phase by sedimentation separation or filtration.
[0045]
According to the above treatment, cyanogen in wastewater can be removed safely and inexpensively by simple procedures while using as little chemicals as possible compared to conventional methods regardless of the type of wastewater such as wastewater containing thiocyanate ion or ammonium ion, the cyanogen concentration (total cyanogen content (mg/L)) can be significantly reduced to at or lower than the effluent standard, and thus wastewater after the treatment can be discharged into sewers or recycled without requiring neutralization treatment.
When the treated wastewater is released as it is, compounds may be added at such amounts that the total cyanogen concentration is reduced at or below the effluent standard in the method of the present invention. When the treated wastewater is diluted in another wastewater before release, the compounds may be added at such amounts that the diluted wastewater has the total cyanogen concentration at or below the effluent standard.
Generally, treated wastewater is released after diluting thereof with another wastewater at plants and the like. It is preferable to control the amounts of active components by taking the cost effectiveness into account.
Thus, it is understood that the present invention encompasses the treatment which does not result in the total cyanogen concentration after the treatment of 1 mg/L or lower such as the treatment which results in the concentration of generally 5 mg/L or less.
EXAMPLES
[0046]
The present invention is specifically described by way of Test Examples which do not limit the present invention.
[0047]
In following Test Example 1-1, cyanogen-containing wastewater A (pH 8.3) was used which was collected from a coke oven wastewater line at an iron mill and had water quality indicated in Table 1.
[0048]
Table 1
[0049]
In following Test Example 1-2, cyanogen-containing wastewater B (pH 7.8) was used which was collected from raw water from a blast furnace dust collector at an iron mill and had water quality indicated in Table 2.
[0050]
Table 2
[0051]
In following Test Examples 2-1, 2-3 and 2-4, cyanogen-containing wastewater C (pH 8.0) was used which was prepared as follows and had water quality indicated in Table 3.
Cyanogen-containing wastewater C was prepared with a potassium ferrocyanide aqueous solution, a potassium cyanide aqueous solution, a potassium thiocyanate aqueous solution, a calcium chloride dihydrate aqueous solution, a sodium chloride aqueous solution, sodium sulfate aqueous solution, ammonium chloride aqueous solution and a sodium hydrogen carbonate aqueous solution.
[0052]
Table 3
[0053]
In following Test Example 2-2, cyanogen-containing wastewater D (pH 8.0) was used which was prepared as follows and had water quality indicated in Table 4.
Cyanogen-containing wastewater D was prepared with a potassium cyanide aqueous solution, a calcium chloride dihydrate aqueous solution, sodium chloride aqueous solution, a sodium sulfate aqueous solution and a sodium hydrogen carbonate aqueous solution.
[0054]
Table 4
[0055] (Test Example 1-1)
To respective 300-mL beakers, 300 mL cyanogen-containing wastewater A was placed, and sodium hypochlorite, manganese chloride and hydrogen peroxide were respectively added thereto so as to obtain the concentrations indicated in Table 5, thereby obtaining water samples.
To some water samples, a sulfuric acid aqueous solution or a sodium hydroxide aqueous solution was added to adjust the pH of the water samples to the values indicated in Table 5.
The obtained water samples were then agitated on an agitator (produced by Miyamoto Corporation, Jar Tester (water sample flocculator), model: MJS-6, shape of agitating blade: double blade, maximum blade diameter: 60 mm) at a rotation speed of 120 rpm for 30 minutes.
The water samples were then measured for the total cyanogen concentration (T-CN) according to JIS KOI02 and the effect of removal of the cyanogen compound in the water samples was evaluated.
In the present test, a blank sample (Comparative Example 4) without sodium hypochlorite, manganese chloride or hydrogen peroxide was tested in parallel.
The obtained results are shown in Table 5 together with the compounds added and the amounts thereof and the pH of water samples.
[0056]
Table 5
1) Effective chlorine concentration 2) Manganese ion concentration [0057]
The test results in Table 5 indicate the following: a combined treatment with sodium hypochlorite and hydrogen peroxide at pH 7 to 9 (Examples 1 to 3) and a combined treatment with sodium hypochlorite, manganese chloride and hydrogen peroxide at pH 8 and 9 (Examples 4 to 7) have a sufficient cyanogen removal effect; on the other hand, a treatment with only sodium hypochlorite (Comparative Example 1) results in an increase in the cyanogen content in treated water compared to the blank (Comparative Example 4) (this may be because of production of cyanogen by oxidation of thiocyanate ion in the wastewater); a treatment according to the alkaline chlorination method (Comparative Example 2) in which an excess amount of sodium hypochlorite was added does not provide a sufficient cyanogen removal effect; and a combined treatment with sodium hypochlorite and manganese chloride (Comparative Example 3), for which the inventors expected to observe a cyanogen removal effect, does not provide a sufficient cyanogen removal effect partly because of an insufficient amount of chemicals added.
[0058] (Test Example 1-2)
To a 1-L beaker, 1 L cyanogen-containing wastewater B was placed and warmed up in a water bath at 55°C. Manganese chloride was added so as to obtain the concentration indicated in Table 6, the mixture was agitated for 2 minutes, and a sulfuric acid aqueous solution or a sodium hydroxide aqueous solution was added to adjust the pH of the water sample to 8.0.
To the obtained water sample, sodium hypochlorite was added so as to obtain the concentration indicated in Table 6 and agitated on an agitator (produced by Miyamoto Corporation, Jar Tester (water sample flocculator), model: MJS-6, shape of agitating blade: double blade, maximum blade diameter: 60 mm) at a rotation speed of 120 rpm for 1 hour.
To the water sample, a sulfuric acid aqueous solution or a sodium hydroxide aqueous solution was added to adjust the pH of the water sample to 8.0. The obtained water sample (1) was measured for the cyanogen content (T-CN) and chemical oxygen demand (CODMn).
[0059]
To the obtained water sample (1), an inorganic flocculant (polyaluminium chloride) was added so as to be 3 mg/L and agitated on the agitator at a rotation speed of 200 rpm for 2 minutes. Further, a polymer flocculant (product name: FLOCKLANT A-1240, produced by Katayama Chemical, Inc.) was added so as to be 1 mg/L and the mixture was agitated on the agitator at a rotation speed of 120 rpm for 30 minutes followed by at a rotation speed of 60 rpm for 1.5 minutes. The obtained water sample was left to stand for 5 minutes followed by observation of the appearance.
The supernatant of the obtained water sample (250 mL) was then collected into a 300-mL beaker and warmed up in a water bath at 55°C. The rest of the supernatant was filtered through a No. 5A filter paper.
To the obtained supernatant water sample, hydrogen peroxide was added so as to obtain the concentration indicated in Table 6, and a sulfuric acid aqueous solution or a sodium hydroxide aqueous solution was added to adjust the pH of the water sample to 8.0, followed by agitation on the agitator at a rotation speed of 120 rpm for 2 hours.
After agitation, the water sample was filtered through a No. 5A filter paper and the water sample (2) was measured for the cyanogen content (T-CN) and the chemical oxygen demand (CODMn).
The obtained results are shown in Table 6.
[0060]
Table 6
1) Effective chlorine concentration 2) Manganese ion concentration [0061]
The test results in Table 6 indicate the following: after the first stage operation, the cyanogen content (T-CN) reduced to about 3 mg/L and the chemical oxygen demand (CODMn) also decreased; and in Examples 8 and 9, after addition of hydrogen peroxide, the cyanogen content (T-CN) was less than 1 mg/L.
[0062] (Test Example 2-1/ One-stage operation test of cyanogen-containing wastewater containing cyano complex)
Cyanogen-containing wastewater C was treated in the same manner process as in Test Example 1 except that the cyanogen-containing wastewater used was cyanogen-containing wastewater C and sodium hypochlorite, manganese chloride and hydrogen peroxide were respectively added so as to obtain the concentrations indicated in Table 7.
To some water samples, a sulfuric acid aqueous solution or a sodium hydroxide aqueous solution was added to adjust the pH of the water samples to the values indicated in Table 7.
Water-insoluble products in the water sample were then filtered out, the total cyanogen concentration (T-CN) in the filtrate was measured according to JIS KOI02 and the removal effect of the cyanogen compound in each water sample was evaluated.
In the present test, a blank sample (Comparative Example 11) without sodium hypochlorite, manganese chloride or hydrogen peroxide was tested in parallel.
The obtained results are shown in Table 7 together with the compounds added and the amounts thereof and the pH of water samples.
[0063]
Table 7
1) Effective chlorine concentration 2) Manganese ion concentration [0064]
The test results in Table 7 indicate the following: when treatment is performed with added compounds in combination of sodium hypochlorite, manganese chloride and hydrogen peroxide at pH 6.5 to 9 (Examples 10 to 16), a sufficient cyanogen removal effect is exhibited; on the other hand, when treatment is performed only with sodium hypochlorite at pH 8 (Comparative Example 5) or treatment is performed only with manganese chloride at pH 8 (Comparative Example 6), a sufficient cyanogen removal effect is not obtained; a combined treatment with sodium hypochlorite and manganese chloride at pH 8 and 9 (Comparative Examples 7 to 9), for which the inventors expected to observe a cyanogen removal effect, does not provide a sufficient effect for the present wastewater; and a treatment only with hydrogen peroxide (Comparative Example 10) in which an excess amount of hydrogen peroxide was added provides little effect.
[0065] (Test Example 2-2/ One-stage operation test of cyanogen-containing wastewater containing cyanide ion)
Cyanogen-containing wastewater D was treated in the same process as in Test Example 2-1 except that the cyanogen-containing wastewater used was cyanogen-containing wastewater D and sodium hypochlorite and hydrogen peroxide were respectively added so as to obtain the concentrations indicated in Table 8.
To some water samples, a sulfuric acid aqueous solution or a sodium hydroxide aqueous solution was added to adjust the pH of the water samples to the values indicated in Table 8.
Water-insoluble products in the water sample were then filtered out, the total cyanogen concentration (T-CN) in the filtrate was measured according to JIS KOI02 and the removal effect of cyanogen compound in each water sample was evaluated.
The obtained results are shown in Table 8 together with the compounds added and the amounts thereof and the pH of water samples.
[0066]
Table 8
1) Effective chlorine concentration 2) Molar equivalent relative to cyanogen content [0067]
The test results in Table 8 indicate the following: when a treatment is performed with added compounds in combination of sodium hypochlorite and hydrogen peroxide at pH 8 (Examples 17 to 19), a sufficient cyanogen removal effect is exhibited.
[0068] (Test Example 2-3/ Two-stage operation test of cyanogen-containing wastewater containing cyano complex)
To respective 300-mL beakers, 300 mL cyanogen-containing wastewater C was placed, and one or two selected from sodium hypochlorite, manganese chloride and hydrogen peroxide were added so as to obtain the concentrations indicated in Table 9, thereby obtaining water samples.
To some water samples, a sulfuric acid aqueous solution or a sodium hydroxide aqueous solution was added to adjust the pH of the water samples to the values indicated in Table 9.
The obtained water samples were then agitated on the agitator at a rotation speed of 120 rpm for 30 minutes.
Water-insoluble products in the water sample were then filtered out, each filtrate (supernatant) was taken in a 200-mL beaker, one or two selected from sodium hypochlorite, manganese chloride and hydrogen peroxide were added so as to obtain the concentrations indicated in Table 9 and the mixture was agitated on the agitator at a rotation speed of 120 rpm for 30 minutes.
The total cyanogen concentration (T-CN) in the water samples was then measured according to JIS KOI02 and the removal effect of the cyanogen compound in each water sample was evaluated.
The obtained results are shown in Table 9 together with the compounds added and the amounts thereof and the pH of water samples.
[0069]
Table 9
1) Effective chlorine concentration 15 2) Manganese ion concentration [0070]
From the test results in Table 9, it is found that even when the chemicals for the method of the present invention are used in two stages, a sufficient cyanogen removal effect is exhibited.
[0071] (Test Example 2-4/ One-stage operation test of cyanogen-containing wastewater containing cyano complex)
Cyanogen-containing wastewater C was treated in the same process as in Test Example 2-1 except that sodium hypochlorite, a metal compound and hydrogen peroxide were respectively added so as to obtain the concentrations indicated in Table 10. The metal compounds used were ferrous chloride tetrahydrate (Fe2+), zinc chloride (Zn2+), cuprous chloride (Cu+) and cupric sulfate pentahydrate (Cu2+).
The obtained results are shown in Table 10 together with the compounds added and the amounts thereof and the pH of water samples.
[0072]
Table 10
1) Effective chlorine concentration 2) Metal ion concentration [0073]
The test results in Table 10 indicate the following: when treatment is performed with added compounds in combination of sodium hypochlorite, a specific metal compound (a compound that can form divalent iron ion in water or a copper compound) and hydrogen peroxide (Examples 27 to 32), a sufficient cyanogen removal effect is exhibited.
Claims (5)
1. A method for treating cyanogen-containing wastewater, comprising adding to cyanogen-containing wastewater a hypochlorite and hydrogen peroxide, simultaneously or separately, to decompose cyanogen in the wastewater and/or produce a water-insoluble compound containing cyanogen, thereby removing cyanogen from the wastewater.
2. The method for treating cyanogen-containing wastewater according to claim 1, wherein the cyanogen-containing wastewater is preliminarily measured for a cyanogen content, and the hypochlorite in terms of effective chlorine concentration and hydrogen peroxide are added at 0.1 molar equivalent or more and 0.1 molar equivalent or more, respectively, relative to the measured content.
3. The method for treating cyanogen-containing wastewater according to claim 1 or 2, wherein the cyanogen-containing wastewater originally contains one or more metal ions selected from manganese ion, iron ion and copper ion.
4. The method for treating cyanogen-containing wastewater according to any one of claims 1 to 3, wherein one or more metal compounds selected from a manganese compound, an iron compound and a copper compound is further added.
5. The method for treating cyanogen-containing wastewater according to any one of claims 1 to 4, wherein the cyanogen-containing wastewater has pH of 9 or lower.
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| JP2016-011576 | 2016-01-25 | ||
| JP2016011576 | 2016-01-25 | ||
| PCT/JP2016/064012 WO2016190108A1 (en) | 2015-05-22 | 2016-05-11 | Method for treating cyanogen-containing wastewater |
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| JP2017104802A (en) * | 2015-12-09 | 2017-06-15 | 日鉄住金環境株式会社 | Method for treating cyanide-containing wastewater |
| JP6547055B2 (en) * | 2017-12-20 | 2019-07-17 | 日鉄環境株式会社 | Method for suppressing formation of cyano complex, method for treating exhaust gas, and exhaust gas treatment system |
| JP7353619B2 (en) * | 2019-07-23 | 2023-10-02 | 株式会社片山化学工業研究所 | Treatment method for cyanide-containing wastewater |
| CN110980916B (en) * | 2019-11-14 | 2021-03-26 | 东北大学 | Method for degrading thiocyanate in cyanogen-containing barren solution under acidic condition |
| JP7440031B2 (en) | 2019-11-14 | 2024-02-28 | 株式会社片山化学工業研究所 | Treatment method for cyanide-containing wastewater |
| CN113800703B (en) * | 2021-11-15 | 2023-06-06 | 大唐环境产业集团股份有限公司 | Catalyst flue gas washing wastewater treatment method and system |
| JP7448129B2 (en) | 2022-07-29 | 2024-03-12 | 株式会社片山化学工業研究所 | How to treat wastewater |
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| JPS51121957A (en) * | 1975-04-18 | 1976-10-25 | Asahi Chem Ind Co Ltd | Method of treating waste liquid |
| JPS5167672A (en) * | 1974-12-10 | 1976-06-11 | Mitsubishi Petrochemical Co | SHIANSAKUIONGANJUHAISUINO SHORIHOHO |
| FR2321455A1 (en) * | 1975-08-22 | 1977-03-18 | Ugine Kuhlmann | NEW OXIDIZING WATER TREATMENT PROCESS |
| JPH0235991A (en) * | 1988-07-22 | 1990-02-06 | Katayama Chem Works Co Ltd | Treatment of waste water containing cyanic compound |
| DE4110055A1 (en) * | 1991-03-27 | 1992-10-01 | Degussa | METHOD FOR DETOXIFYING CYANIDIC AQUEOUS SOLUTIONS |
| US5792336A (en) * | 1995-09-18 | 1998-08-11 | Elif Technologies Ltd. | Method for purification of wastewater from soluble substances |
| JPH1133571A (en) * | 1997-07-17 | 1999-02-09 | Kurita Water Ind Ltd | Wastewater treatment method |
| JP4106415B2 (en) * | 2000-04-21 | 2008-06-25 | 株式会社片山化学工業研究所 | Treatment method of wastewater containing cyanide |
| JP2004074087A (en) * | 2002-08-21 | 2004-03-11 | Mitsubishi Gas Chem Co Inc | Treatment method for cyanogen compound-containing waste liquid |
| JP4382556B2 (en) | 2004-03-30 | 2009-12-16 | Ｊｆｅスチール株式会社 | Treatment method of wastewater containing cyanide |
| CN101274806B (en) * | 2007-03-30 | 2010-09-29 | 北京清华紫光英力化工技术有限责任公司 | Novel process for reclaiming waste water containing CN- and NH3 or NH4- |
| JP5179242B2 (en) * | 2008-04-15 | 2013-04-10 | 住友重機械エンバイロメント株式会社 | Waste water treatment method and waste water treatment equipment |
| JP2012157798A (en) | 2011-01-31 | 2012-08-23 | Jfe Steel Corp | Method for treating cyanide-containing wastewater |
| CN102329026B (en) | 2011-09-07 | 2012-10-03 | 南昌市国昌环保科技有限公司 | Treatment method of coking wastewater subjected to biochemical treatment |
| CN104163518B (en) * | 2014-05-15 | 2016-07-06 | 浙江海洋学院 | A kind of processing method of cyanide wastewater of printing and dyeing |
| CN104261548A (en) * | 2014-10-17 | 2015-01-07 | 苏州新协力环保科技有限公司 | Novel oxidation treatment method for chemical waste water |
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