CN102883783B - Chemical substance degraded inorganic agent containing persulfate and silver complex and employ its biodegrading process of chemical substance - Google Patents

Chemical substance degraded inorganic agent containing persulfate and silver complex and employ its biodegrading process of chemical substance Download PDF

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Publication number
CN102883783B
CN102883783B CN201180021291.7A CN201180021291A CN102883783B CN 102883783 B CN102883783 B CN 102883783B CN 201180021291 A CN201180021291 A CN 201180021291A CN 102883783 B CN102883783 B CN 102883783B
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silver
chemical substance
persulfate
inorganic agent
biodegrading process
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CN102883783A (en
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吉冈成康
君塚健一
吉田净
海老原孝
新开洋介
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/36—Detoxification by using acid or alkaline reagents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
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    • C07—ORGANIC CHEMISTRY
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
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    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages

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Abstract

Problem of the present invention is to provide safety and degrade efficiently chemical substance and chemical substance degraded inorganic agent useful economically and employ its biodegrading process of chemical substance.The present invention relates to chemical substance degraded inorganic agent and employ its biodegrading process of chemical substance, the feature of described chemical substance degraded inorganic agent is, it is the inorganic agent for chemical substance of degrading, containing persulfate and silver complex.

Description

Chemical substance degraded inorganic agent containing persulfate and silver complex and employ its biodegrading process of chemical substance
Technical field
The present invention relates to the chemical substance degraded inorganic agent containing persulfate and silver complex and employ its biodegrading process of chemical substance.
Background technology
Need the region of report when having process to be designated as to need region to be processed, Character change as the soil great majority of the history of the chemical substance of the object of Japanese soil temperature and soil moisture content, such as VOC, cyanide and/or metal cyanide complex, form social concern.In addition, the products from crude oil as the object of Japanese oil pollution guide cause the generation of oil pollution, form and produce dysgenic reason to living environment.For cyanide herein, include, for example out the cyanide of the generation cyanide ion of hydrogen cyanide, Cymag and so on.In addition, for metal cyanide complex, include, for example the cyano complex that taps a blast furnace, the ion of copper cyano complex and salt thereof.
For the processing method of the chemical substance of the object as Japanese soil temperature and soil moisture content or preventing and treating pollution of oil guide, in-situ oxidation edman degradation Edman, biological prosthetic, Powder by Iron Powder etc. can be listed.In-situ oxidation edman degradation Edman is the method catalyst combination such as persulfate, this oxidant of hydrogen peroxide and iron being carried out purifying, but is difficult to the material of this refractory organics of degraded carrene.In addition, this material of degraded carrene is also difficult to bioanalysis, Powder by Iron Powder.
As the processing method of cyanogen, the method such as chlor-alkali, acid volatilization absorption method, flocculent precipitation, hydro-thermal reaction method can be listed.
Chlor-alkali is following method: make handling object thing be in the alkaline state of more than pH10, then adds the oxidants such as chlorine, hypochlorous acid, potassium permanganate and carries out oxidative degradation (see non-patent literature 1).But the cyanide being easier to degrade although the method can be degraded, is difficult to the metal cyanide complex that degraded six cyanogen closes the refractory organics of ferrous acid radical ion and so on.
Flocculent precipitation to be applied to the processing method (see non-patent literature 2) processing and be difficult to the cyanogen of the metal cyanide complex of the refractory organics of oxidative degradation.Such as, by adding excessive iron ion, copper ion or zinc ion in the waste water containing six cyanogen conjunction ferrous acid radical ions, insoluble six cyanogen can be generated and close the precipitation of the heavy metallic salt of ferrous acids and be separated removal from waste water.But, because this facture makes cyanogen form infusible precipitate to carry out being separated and the technology of non-degradable, the purified in situ method of soil therefore cannot be applied to.
Acid volatilization absorption method generates hydrogen cyanide and the method removed of volatilizing in gaseous form by making handling object thing be in the acid state of below pH3.But because hydrogen cyanide is widely known by the people as severe toxicity, therefore security existing problems, have problems when particularly processing soil and/or underground water in position.In addition, also exist by making soil be the acidity of below pH3 and make the heavy metal component stripping in soil thus produce the secondary pollution caused by heavy metal, the anxiety occurring as the reinforcing bar of underground structure, the corrosion of underground piping.
Hydro-thermal reaction method be by under elevated pressure, more than the 150 DEG C technology (see patent document 1) metal cyanide complex being processed to cyanogen of degrading.But this facture needs handling object thing to move in pressure vessel to process, and is therefore difficult to be applied to purified in situ.
Relative to these, Patent Document 2 discloses and to degrade the method for cyanogen by carrying out oxidation processes with the high temperature of more than 80 DEG C to the object containing metal cyanide complex.But, economy is difficult to a large amount of soil and/or underground water are heated to high temperature in position and maintain, is therefore difficult to be applied to purified in situ.
Patent Document 3 discloses and use the ozone with high oxidation power by the method containing the cyanogen degraded in the object of metal cyanide complex.But, use poisonous ozone not only existence can produce the anxiety of harmful effect to the ecosystem, and need after process to carry out degradation treatment to residual ozone, therefore there is the shortcoming that facility load is heavy.
Also biodegradation method is attempted, but existence is difficult to the shortcoming being applied to the pollution containing the virose cyanogen of tool with high concentration.
In addition, to Patent Document 4 discloses while conversion zone is remained on more than pH5 and in the scope of 100 ~ 1000mg/L, to add persulfate by the method for the pollutant purification by chemical contamination.But, although be effective by adding the purification carried out of persulfate for chemical substances such as organochlorine compounds, the metal cyanide complex of the refractory organics that is difficult to degrade.
prior art document
patent document
Patent document 1: Japanese Patent Publication 55-50718 publication
Patent document 2: Japanese Laid-Open Patent Publication 50-118962 publication
Patent document 3: Japanese Unexamined Patent Publication 2000-153284 publication
Patent document 4: Japanese Patent No. 4027209 publications
Non-patent literature
Non-patent literature 1: plating technique guide revised edition (め つ き Ji Intraoperative ガ イ De changes Order version), Japanese gilding synergistic combination, 2004,496 pages
Non-patent literature 2: plating technique guide revised edition (め つ き Ji Intraoperative ガ イ De changes Order version), Japanese gilding synergistic combination, 2004,497 pages
Summary of the invention
the problem that invention will solve
The object of the invention is to solve at least one in the various problems of above-mentioned this prior art, provide safety and degrade efficiently chemical substance and chemical substance degraded inorganic agent useful economically and employ its biodegrading process of chemical substance.
for the scheme of dealing with problems
The present inventor etc. conduct in-depth research to solve the problem, and found that, by using the inorganic agent containing persulfate and silver complex, the chemical substance of refractory organics of can easily degrading, thus complete the present invention.
That is, above-mentioned problem can be solved by following the present invention.
<1> an embodiment of the invention are a kind of chemical substance degraded inorganic agents, and it is characterized in that, it is the inorganic agent for chemical substance of degrading, containing persulfate and silver complex.
<2> preferred embodiment of the present invention is the inorganic agent described in above-mentioned <1>, it is characterized in that, at least one that aforementioned silver complex is selected from the group be made up of the compound containing pyridine ring, the compound containing pyrimidine ring, compound, hydroxycarboxylic acid, amino acids and the diaminopropanes containing ethylenediamine structure is formed as complexing agent.
<3> another preferred embodiment of the present invention is the inorganic agent described in above-mentioned <2>, it is characterized in that, aforementioned silver complex is selected from by 2,2 '-bipyridyl, 2-aminomethyl-pyridine, terpyridyl, pyridine carboxylic acid, 2-pyridine ethanol, 3-aminopyridine, 2-aminopyrimidine, ethylenediamine, tetramethylethylenediamine, ethylenediamine tetra-acetic acid, lactic acid, glycolic, 1, at least one in the group of 2-diaminopropanes, 1,3-diaminopropanes and glycine composition is formed as complexing agent.
<4> another embodiment of the present invention is a kind of chemical substance degraded inorganic agent, and it is characterized in that, it is the inorganic agent for chemical substance of degrading, containing persulfate, silver compound and complexing agent.
<5> preferred embodiment of the present invention is the inorganic agent described in above-mentioned <4>, wherein, foregoing complexing agents is for being selected from by 2,2 '-bipyridyl, 2-aminomethyl-pyridine, terpyridyl, pyridine carboxylic acid, 2-pyridine ethanol, 3-aminopyridine, 2-aminopyrimidine, ethylenediamine, tetramethylethylenediamine, ethylenediamine tetra-acetic acid, lactic acid, glycolic, 1, at least one in the group of 2-diaminopropanes, 1,3-diaminopropanes and glycine composition.
<6> preferred embodiment of the present invention is the inorganic agent described in above-mentioned <4> or <5>, wherein, aforementioned silver compound is be selected from least one in the group that is made up of silver nitrate, silver sulfate, silver nitrite, silver sulfite, silver carbonate, silver orthophosphate, boric acid silver, silver acetate, silver oxalate, silver citrate and silver oxide.
<7> another preferred embodiment of the present invention is the inorganic agent according to any one of above-mentioned <1> ~ <6>, wherein, aforementioned persulfate is peracetic dithionite.
<8> another preferred embodiment of the present invention is the inorganic agent according to any one of above-mentioned <1> ~ <7>, and it is also containing sulfate.
<9> another preferred embodiment of the present invention is the inorganic agent according to any one of above-mentioned <1> ~ <8>, wherein, afore mentioned chemical material is cyanide and/or metal cyanide complex.
<10> another embodiment of the present invention is the biodegrading process of chemical substance, it is characterized in that, it makes the inorganic agent according to any one of above-mentioned <1> ~ <8> contact with chemical substance, and described chemical substance contains at least one in VOC, products from crude oil, cyanide or metal cyanide complex.
<11> preferred embodiment of the present invention is the biodegrading process described in above-mentioned <10>, it is characterized in that, the pH of the afore mentioned chemical material in process is remained on 4 ~ 11.
<12> another preferred embodiment of the present invention is the biodegrading process described in above-mentioned <10> or <11>, it is characterized in that, also add pH adjusting agent.
<13> another preferred embodiment of the present invention is the biodegrading process described in above-mentioned <12>, and wherein, aforementioned pH adjusting agent is acetate type buffer.
<14> another preferred embodiment of the present invention is the biodegrading process described in above-mentioned <13>, and wherein, aforementioned acetate type buffer is acetic acid and/or sodium acetate.
<15> another preferred embodiment of the present invention is the biodegrading process according to any one of above-mentioned <10> ~ <14>, it is characterized in that, make the temperature of the afore mentioned chemical material in process be up to 70 DEG C.
<16> another preferred embodiment of the present invention is the biodegrading process according to any one of above-mentioned <10> ~ <15>, wherein, afore mentioned chemical material is the combination of one or more materials be selected from the group that is made up of soil, underground water, waste water and discarded object.
<17> another preferred embodiment of the present invention is the biodegrading process according to any one of above-mentioned <10> ~ <16>, it is characterized in that, when afore mentioned chemical material contains cyanide and/or metal cyanide complex, use relative to the inorganic agent of the cyanide 1.0mgCN in afore mentioned chemical material at least containing 0.1g persulfate.
<18> another preferred embodiment of the present invention is the biodegrading process according to any one of above-mentioned <10> ~ <17>, it is characterized in that, aforementioned processing agent and afore mentioned chemical material are uniformly mixed.
the effect of invention
According to the chemical substance degraded inorganic agent of preferred embodiment of the present invention and the biodegrading process of chemical substance employing it, there is following effect.
(1) there is high oxidizing force, the chemical substance such as cyanide, metal cyanide complex, carrene being difficult to oxidative degradation of can securely and effectively degrading.
(2) to degrade while the pH of the chemical substance as object is remained near neutral cyanogen, therefore, it is possible to degraded cyanide, metal cyanide complex and do not produce hydrogen cyanide and not stripping heavy metal component.
(3) when by as the chemical substance of object and the polluted soil such as cyanide, metal cyanide complex and/or underground water, oxidative degradation can be carried out in position.
Therefore, according to the present invention, securely and effectively can degrade and form the chemical substance such as cyanide, metal cyanide complex of pollution cause.
Detailed description of the invention
Below describe the present invention in detail.
An embodiment of the invention are a kind of chemical substance degraded inorganic agents, and it is characterized in that, it is the inorganic agent for chemical substance of degrading, containing persulfate and silver complex.Replace above-mentioned silver complex, also can be containing silver compound and complexing agent and form the material of silver complex when using inorganic agent.
Chemical substance of the present invention is the chemical substance of the pollution cause forming soil, underground water, waste water and discarded object etc., is the material specified in the Japanese soil temperature and soil moisture content such as VOC, cyanide, metal cyanide complex; Because of oil film oil gas taste by the products from crude oil of guide specification.Cyanide of the present invention refers to the compound by dissociating with cyanide ion.As cyanide, include, for example out hydrogen cyanide, Cymag, potassium cyanide etc.Metal cyanide complex refers to and produces the complex compound of cyanide ion, cyanide or hydrogen cyanide and the salt of complex compound by dissociating.Include, for example out six cyanogen and close iron cyano complex, copper cyano complex, zinc cyano complex, nickel cyano complex, silver-colored cyano complex, cobalt cyano complex, the gold-cyanide complexs etc. such as ferrous acid radical ion, Hexacyanoferrate radical ion, five cyanogen conjunction nitrosyl ferrous acid radical ions.As VOC of the present invention, include, for example out 1,1-dichloroethylene, cis-1,2-dichloroethylene, trichloro-ethylene, tetrachloro-ethylene, 1,3-dichloropropylene, carrene, 1,2-dichloroethanes, 1,1,1-trichloroethanes, 1,1,2-trichloroethanes, carbon tetrachloride, benzene etc.As products from crude oil of the present invention, include, for example out light oil, kerosene, gasoline, heavy oil etc.
Inorganic agent of the present invention can be applied to the object containing chemical substance.As object, the solid containing chemical substance, liquid or slurries can be listed.Object can in its part containing gas.Include, for example out one or more the combination be selected from soil, underground water, waste water and discarded object, but be not limited to these 4 kinds.
Persulfate in inorganic agent of the present invention is not particularly limited, such as, can uses sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate etc.From the size of the solubility in water, preferred sodium peroxydisulfate and ammonium persulfate, never there is the anxiety causing secondary pollution by ammonia nitrogen, more preferably sodium peroxydisulfate.And then, in persulfate, preferably use peracetic dithionite, especially, preferably use sodium peroxydisulfate.The form of adding persulfate is not particularly limited, the aqueous solution, suspension, powder, aerosol etc. can be used.Can the consumption of persulfate can to purify object for index by the test of purification property, suitable amount is selected according to the content of the chemical substance in object, and when chemical substance is cyanide, preferably be at least 0.1g relative to the cyanide 1.0mgCN in object, be more preferably more than 0.2g, most preferably be more than 0.5g.Consider economy and slow down the change of pH of object, the upper limit of the consumption of persulfate is preferably below 50g relative to 1kg object, is more preferably below 20g, most preferably is below 10g.Herein, cyanide amount can be obtained by total cyanogen concentration that record according to " the total cyanogen of 38.1.2 (TotalCyanogen) " and " 38.34-pyridine carboxylic acid-pyrazolone absorption photometry (PyridinecarboxylicAcid-PyrazoloneAbsorptiometry) " of JISK0102:2008.
Complexing agent for the formation of silver complex of the present invention is not particularly limited, is preferably selected from the compound in the compound containing pyridine ring, the compound containing pyrimidine ring, compound, hydroxycarboxylic acid, amino acids and the diaminopropanes containing ethylenediamine structure.
As the compound containing pyridine ring, include, for example out 2,2 '-bipyridyl, 2-aminomethyl-pyridine, terpyridyl, pyridine carboxylic acid, 2-pyridine ethanol, 3-aminopyridine, 2-aminopyrimidine, 2-(amino methyl) pyridine etc.
As the compound containing pyrimidine ring, include, for example out 2-aminopyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4,6-dimethyl pyrimidines, 2,4-Dimethylaminopyrimidine etc.
As the compound containing ethylenediamine structure, include, for example out ethylenediamine, tetramethylethylenediamine, ethylenediamine tetra-acetic acid, 1,2-diaminopropanes, hydroxyethylethylene diamine tri-acetic acid, diethylenetriamine pentaacetic acid, teiethylene tetramine-hexacetic acid etc.
As hydroxycarboxylic acid, include, for example out lactic acid, malic acid, glycolic, tartaric acid, citric acid, gluconic acid, grape saccharic acid etc.
As amino acids, include, for example out glycine, alanine, aspartic acid, NTA, 1,3-trimethylen-edinitrilo-tetraacetic acid etc.
Complexing agent of the present invention is more preferably and is selected from 2,2 '-bipyridyl, 2-aminomethyl-pyridine, terpyridyl, pyridine carboxylic acid, 2-pyridine ethanol, 3-aminopyridine, 2-aminopyrimidine, ethylenediamine, tetramethylethylenediamine, ethylenediamine tetra-acetic acid, lactic acid, glycolic, 1,2-diaminopropanes, 1, more than one in 3-diaminopropanes and glycine, be particularly preferably 2,2 '-bipyridyl.
In addition, as long as the silver compound used in silver complex can form silver complex with above-mentioned complexing agent and then be not particularly limited, include, for example out silver nitrate, silver sulfate, silver nitrite, silver sulfite, silver carbonate, silver orthophosphate, boric acid silver, silver acetate, silver oxalate, silver citrate, silver oxide etc., wherein, silver nitrate, silver sulfate, silver acetate and silver oxide is suitably.As long as the silver compound in silver complex of the present invention is then not particularly limited in the scope not damaging effect of the present invention with the compounding ratio of complexing agent, as the mol ratio (complexing agent/silver ion) of complexing agent relative to silver compound (by silver ion), be preferably 0.2 ~ 3, be more preferably 0.5 ~ 3, most preferably be 0.5 ~ 2.Make complexing agent too much can run counter to economy, if make mol ratio too small, the precipitation of silver salt can be produced and not preferred.
The form of adding silver complex is not particularly limited, the aqueous solution, suspension, powder, aerosol etc. can be used.Can the consumption of silver complex can to purify object for index by the test of purification property, suitable amount is selected according to the content of the chemical substance in object, when chemical substance is cyanide, preferably be at least 0.1mgAg relative to the cyanide 1.0mgCN in object, be more preferably more than 0.5mgAg, most preferably be more than 1.0mgAg.Consider economy, the upper limit of the consumption of silver complex is preferably below 100mgAg relative to 1kg object, is more preferably below 40mgAg, most preferably is below 10mgAg.
Inorganic agent of the present invention contains persulfate and silver complex, or containing persulfate and silver compound and complexing agent, and persulfate and silver complex (or silver compound and complexing agent) can be pre-mixed, also can at the forward slip value being about to use.In addition, also the aqueous solution individually containing them can be about to the forward slip value of use.
The sulfate used in the present invention is not limited, in order to emissions reduction, to the kind of the material in environment, it is desirable to cation type identical with used persulfate as far as possible.Such as, when selected sodium peroxydisulfate is as cleanser, preferably selected sodium sulphate is as sulfate.Relative to persulfate 100 weight portion, the sulfate amount used together with persulfate is at least 1 weight portion, is preferably 1 ~ 20 weight portion, more preferably 1 ~ 10 weight portion.If be less than 1 weight portion, then cannot be promoted the effect of degradation of pollutant, even and if excessive supply also cannot obtain the effect of expected degree, be therefore not preferred economically.
In the present invention, the chemical substance of degrading in object can be contacted by making above-mentioned inorganic agent with the object containing chemical substance.In order to make above-mentioned inorganic agent and object high-efficient contact promote to degrade, it is also effective for inorganic agent and object being uniformly mixed by force.In addition, when the chemical substance concentration height of object, also above-mentioned inorganic agent can be repeated to add in object processing.
In cyanide in object and/or the degraded of metal cyanide complex, preferably the pH of the object in process is remained on 4 ~ 11.If degrade cyanide and/or metal cyanide complex under the state that the pH of object is low, then there is the anxiety producing hydrogen cyanide, under the state that pH is high, then there is the insoluble silver oxide precipitates of generation, cyanogen degrades incomplete anxiety.And then, from the angle of environmental protection, the preferably time enforcement in pH4 ~ 9.
At the pH of object along with the interpolation of medicament, the carrying out of degraded and when changing, in order to the pH of object is remained on 4 ~ 11, can pH adjusting agent be used.In the present invention, owing to using the inorganic agent containing persulfate, the pH of object can reduce along with the carrying out of degraded sometimes, is therefore suitable for adding pH adjusting agent.PH adjusting agent is not particularly limited, the combination of alkali compounds and/or alkali compounds and acid compound can be used, can preferably use the compound group being called as pH buffer.As pH buffer, lemon acids, phosphoric acid class, boric acid class, carbonic acid class, acetate type buffer etc. can be listed, wherein, preferred acetate type buffer.As acetate type buffer, lithium acetate, sodium acetate, potassium acetate, calcium acetate, magnesium acetate etc. can be used.Wherein, from the angle of economy, preferably use sodium acetate and/or acetic acid.Sodium acetate can use any one in trihydrate, anhydride.
In the degraded of the chemical substance utilizing inorganic agent of the present invention to carry out, even if heating target thing can not degraded chemical substance efficiently yet.Therefore, if use inorganic agent of the present invention, then there is no need for the auxiliary device of heating target thing, and the purified in situ of soil and/or underground water can be suitably used for, therefore industrially highly beneficial.When needs carry out rapidly degradation treatment, also can heating target thing, and, economy dangerous from the view point of the operation brought by operation thermal source, further contemplate object be cyanide and/or metal cyanide complex time there is the anxiety etc. producing hydrogen cyanide because of heating, the temperature of object is up to 70 DEG C, is more preferably less than 50 DEG C.
The biodegrading process of chemical substance of the present invention can be suitably used for soil and/or underground water purification in position.The method of adding above-mentioned inorganic agent and pH adjusting agent in subtend soil and/or underground water is not particularly limited, and can use injection, press-in, injection, stirring, natural diffuseness, infiltration, injected system is added to drawing water.In addition, also can by carry out in the position being different from point of addition aspirating, reduce pressure control to add speed, direction.
Embodiment
Illustrate that embodiment specifically describes the present invention further below.But the present invention is also not limited by the following examples.In addition, the concentration of persulfate is obtained by permanganimetric method.
Embodiment 1
In pure water, dissolve six cyanogen close ferrous acid potassium (special grade chemical that little Zong chemicals Co., Ltd. manufactures), preparation concentration is the simulating pollution water of 10mgCN/L.Using as 2 of complexing agent, 2 '-bipyridyl (special grade chemical that Wako Pure Chemical Industries, Ltd. manufactures) is dissolved in aqueous sulfuric acid, preparation 0.16 % by weight sulfuric acid 2,2 '-bipyridyl aqueous solution.Silver nitrate (special grade chemical that little Zong chemicals Co., Ltd. manufactures) as silver compound is dissolved in pure water and prepares silver nitrate aqueous solution, mix above-mentioned sulfuric acid 2,2 '-bipyridyl aqueous solution, prepares silver-2, the 2 '-bipyridyl complexes aqueous solution as silver complex.50.0g simulating pollution water is added in glass sample preparation QC, after the sodium acetate trihydrate (special grade chemical that little Zong chemicals Co., Ltd. manufacture) of 1.36g as pH adjusting agent and the sodium peroxydisulfate (sodium peroxydisulfate, extra pure reagent that little Zong chemicals Co., Ltd. manufactures) as persulfate dissolve, mix above-mentioned silver-2,2 '-bipyridyl complexes aqueous solution, at room temperature, dark place leave standstill 6 days.The persulfate concentration before and after leaving standstill and total cyanogen concentration is measured by following method.Result is shown in table 1.
The mensuration > of < persulfate concentration
The residual rate of persulfate is calculated by the persulfate concentration of standing front and back.Persulfate concentration is measured by the back titration of the following stated.
(1) get the ferrous aqueous solution of ammonium sulfate in beaker, after appropriate interpolation aqueous sulfuric acid, use potassium permanganate solution titration, thus measure the concentration of the ferrous aqueous solution of ammonium sulfate.
(2) the ferrous aqueous solution of ammonium sulfate and the sample containing persulfate is got in beaker.Now, getting relative to persulfate is excessive ammonium sulfate ferrous iron.
(3) aqueous sulfuric acid is added in right amount.
(4) potassium permanganate solution titration is used.
The mensuration > of the total cyanogen concentration of <
Measure the total cyanogen concentration before and after leaving standstill.Total cyanogen concentration following methods measures.Time in treatment fluid after leaving standstill containing precipitation, using the value that measures divided by treatment fluid by the summation of total cyanogen amount contained in precipitation and supernatant as total cyanogen concentration.
(1) sample is taken in beaker, dilutes with pure water as required.
(2) ascorbic acid of 10 of the persulfate contained in sample times of equivalents is added with the form of 10 % by weight aqueous ascorbic acids, remove persulfate.
(3) for eliminating the total cyanogen concentration contained in the sample of persulfate, " the total cyanogen of 38.1.2 " and " 38.34-pyridine carboxylic acid-pyrazolone absorption photometry " according to JISK0102:2008 measures.In addition, in the aforementioned mensuration according to JIS, total cyanogen concentration be quantitatively limited to 0.1mgCN/L.
Embodiment 2 ~ 4
As complexing agent, 2-aminomethyl-pyridine (reagent that Tokyo HuaCheng Industry Co., Ltd manufactures), ethylenediamine (special grade chemical that Wako Pure Chemical Industries, Ltd. manufactures) or tetramethylethylenediamine (reagent that Sigma-AldrichCo.LLC. manufactures) is used to replace 2,2 '-bipyridyl, in addition, test similarly to Example 1.The results are shown in table 1.
Comparative example 1
Do not add silver-2, the 2 '-bipyridyl complexes aqueous solution as silver complex, in addition, test similarly to Example 1.Result is shown in table 1.
Comparative example 2
Be not used as the sulfuric acid 2 of complexing agent, 2 '-bipyridyl aqueous solution, replace silver complex and silver nitrate aqueous solution is mixed in contaminant water, in addition, testing similarly to Example 1.Result is shown in table 1.
[table 1]
As shown in table 1, being used as inorganic agent of the present invention by adding persulfate and silver compound and the complexing agent containing pyridine ring or ethylenediamine structure, facilitating the degraded of cyanide.Especially, in the use 2 of embodiment 1, when 2 '-bipyridyl is as complexing agent, display can be degraded cyanide effectively.
Comparative example 3 ~ 4
Mixing FeSO47H2O (special grade chemical that Wako Pure Chemical Industries, Ltd. manufactures) and sulfuric acid 2,2 '-bipyridyl aqueous solution, prepares the iron complex aqueous solution.In addition, mixing potassium permanganate (the rigorous analysis reagent that Wako Pure Chemical Industries, Ltd. manufactures) and sulfuric acid 2,2 '-bipyridyl aqueous solution, prepares the manganese complex aqueous solution.Then, use the aforementioned iron complex aqueous solution or the aforementioned manganese complex aqueous solution to replace the silver complex aqueous solution of embodiment 1, make time of repose be 5 days, in addition, test similarly to Example 1.Result is shown in table 2.
[table 2]
As shown in Table 2, when with the addition of persulfate and iron complex or persulfate and manganese complex, cyanide of substantially cannot degrading.
Embodiment 5 ~ 7
As pH adjusting agent, citrate trisodium dihydrate (special grade chemical that little Zong chemicals Co., Ltd. manufactures), disodium hydrogen phosphate dihydrate or sodium acid carbonate (special grade chemical that little Zong chemicals Co., Ltd. manufactures) is used to replace sodium acetate trihydrate, time of repose is made to be 2 days, 6 days or 4 days, in addition, test similarly to Example 1.Result is shown in table 3.
[table 3]
As shown in table 3, acetate type, lemon acids, phosphoric acid class and carbonic acid class buffer can be used in biodegrading process of the present invention as pH adjusting agent.Especially, using sodium acetate as the embodiment 1 of pH adjusting agent and using sodium acid carbonate as in the embodiment 7 of pH adjusting agent, the degradation effect of cyanide is higher.
Embodiment 8 ~ 9
Change the addition of silver complex, in addition, test similarly to Example 1.Result is shown in table 4.
Embodiment 10 ~ 11
Change the addition of the concentration of simulating pollution water, sodium peroxydisulfate, silver complex and pH adjusting agent, in addition, test similarly to Example 1.Result is shown in table 4.
[table 4]
As shown in table 4, be set as in the system of more than 0.2mgAg by silver complex relative to the consumption of 1.0mgCN cyanide, the degraded of cyanide obtains promotion.When silver complex is set as 1.0mgAg relative to the consumption of 1.0mgCN cyanide, leaves standstill after 6 days, cyanide degradation is less than 0.1mgCN/L to the total cyanogen concentration meeting environmental standard (the relevant environment standard of soil pollution).
Embodiment 12 ~ 14
Change the addition of the addition as the sodium peroxydisulfate of persulfate and the sodium acetate trihydrate as pH adjusting agent, in addition, test similarly to Example 1.Result is shown in table 5.
[table 5]
As shown in table 5, be set as in the system of more than 0.2g by persulfate relative to the consumption of 1.0mgCN cyanide, the degraded of cyanide obtains promotion.When persulfate is set as more than 0.5g relative to the consumption of 1.0mgCN cyanide, leaves standstill after 6 days, cyanide degradation is less than 0.1mgCN/L to the total cyanogen concentration meeting environmental standard (the relevant environment standard of soil pollution).
Embodiment 15 ~ 17
When preparing the silver complex aqueous solution, change the silver nitrate aqueous solution as silver compound and the sulfuric acid as complexing agent 2, the concentration of 2 '-bipyridyl aqueous solution, in addition, tests similarly to Example 1.Result is shown in table 6.
[table 6]
As shown in table 6, when the mol ratio of complexing agent/silver ion is set as more than 0.5 times, leaves standstill after 6 days, cyanide degradation is less than 0.1mgCN/L to the total cyanogen concentration meeting environmental standard (the relevant environment standard of soil pollution).
Embodiment 18
As persulfate, use ammonium persulfate (special grade chemical that Kanto Kagaku K. K. manufactures) to replace sodium peroxydisulfate, in addition, test similarly to Example 13.The results are shown in table 7.
[table 7]
As shown in table 7, when using ammonium persulfate as inorganic agent of the present invention, same with using the situation of sodium peroxydisulfate, the degradation effect of cyanide is good.
Embodiment 19
In pure water, dissolve carrene (special grade chemical that little Zong chemicals Co., Ltd. manufactures), preparation concentration is the simulating pollution water of 19mg/L.Using as 2 of complexing agent, 2 '-bipyridyl (special grade chemical that Wako Pure Chemical Industries, Ltd. manufactures) is dissolved in aqueous sulfuric acid, preparation 0.16 % by weight sulfuric acid 2,2 '-bipyridyl aqueous solution.Silver nitrate (special grade chemical that little Zong chemicals Co., Ltd. manufactures) as silver compound is dissolved in pure water and prepares silver nitrate aqueous solution, mix above-mentioned sulfuric acid 2,2 '-bipyridyl aqueous solution, prepares silver-2, the 2 '-bipyridyl complexes aqueous solution as silver complex.
In the withstand voltage screw socket bottle of glass system (not containing the volume of stirrer: 131mL), sodium acid carbonate (special grade chemical that the little Zong chemicals Co., Ltd. manufactures) aqueous solution added as pH adjusting agent reaches 0.1M to make it, after dissolving the sodium peroxydisulfate (sodium peroxydisulfate, extra pure reagent that little Zong chemicals Co., Ltd. manufactures) as persulfate, load 100mL simulating pollution water, mix above-mentioned silver-2,2 '-bipyridyl complexes aqueous solution, further pure water is filled it up with to bottleneck, cover tightly, at room temperature stir 2 days.Measure the persulfate concentration before and after leaving standstill and concentration dichloromethane.Concentration dichloromethane passes through Headspace Gas Chromatography.Result is shown in table 8.In addition, each concentration is adjusted to normal concentration in whole system (131mL).
Embodiment 20 ~ 31
As complexing agent, use the complexing agent shown in table 8 to replace 2,2 '-bipyridyl, in addition, tests similarly to Example 19.Result is shown in table 8.
Comparative example 5
Be not used as silver-2,2 '-bipyridyl complexes aqueous solution of silver complex, in addition, test similarly to Example 19.Result is shown in table 8.
Comparative example 6
Be not used as silver-2,2 '-bipyridyl complexes aqueous solution of silver complex, replace use silver nitrate aqueous solution, in addition, tests similarly to Example 19.Result is shown in table 8.
[table 8]
As shown in table 8, when employing the inorganic agent containing sodium peroxydisulfate and silver complex of the present invention, the degradation effect of carrene is good.
Embodiment 32
As pH adjusting agent, dissolve 3.40g sodium acetate trihydrate and replace dissolving 1.36g sodium acetate trihydrate, time of repose is set as over 2 days, replace 6 days, in addition, tests similarly to Example 1.The results are shown in table 9.
Embodiment 33
Replace the silver-2 mixed after dissolving as the sodium acetate trihydrate of pH adjusting agent and the sodium peroxydisulfate as persulfate as silver complex, the operation of 2 '-bipyridyl complexes aqueous solution, change into and dissolve sodium acetate trihydrate, then combined silver-2,2 '-bipyridyl complexes aqueous solution, further dissolving sodium peroxydisulfate, in addition, tests in the same manner as embodiment 32.The results are shown in table 9.
Embodiment 34
In pure water, dissolve six cyanogen close ferrous acid potassium, preparation concentration is the simulating pollution water of 20mgCN/L.Using as 2 of complexing agent, 2 '-bipyridyl is dissolved in aqueous sulfuric acid, preparation 0.16 % by weight sulfuric acid 2,2 '-bipyridyl aqueous solution.Preparing silver nitrate aqueous solution using being dissolved in pure water as the silver nitrate of silver compound, mixing above-mentioned sulfuric acid 2,2 '-bipyridyl aqueous solution, preparing silver-2, the 2 '-bipyridyl complexes aqueous solution as silver complex.In glass sample preparation QC, load 25.0g simulating pollution water, dissolve the sodium acetate trihydrate (special grade chemical that little Zong chemicals Co., Ltd. manufacture) of 1.36g as pH adjusting agent.Above-mentioned silver-2 is being mixed using in the sodium persulfate aqueous solution be dissolved in as the sodium peroxydisulfate (little Zong chemicals Co., Ltd. manufacture sodium peroxydisulfate, extra pure reagent) of persulfate in 25.0g pure water, 2 '-bipyridyl complexes aqueous solution, is then mixed into total amount rapidly and is dissolved with in the simulating pollution water of sodium acetate trihydrate.At room temperature, dark place leaves standstill 2 days.The persulfate concentration before and after leaving standstill and total cyanogen concentration is measured by said method.Result is shown in table 9.
Embodiment 35
Use 2-aminomethyl-pyridine to replace 2,2 '-bipyridyl, as complexing agent, in addition, is tested in the same manner as embodiment 32.Result is shown in table 9.
Embodiment 36
Use 2-aminomethyl-pyridine to replace 2,2 '-bipyridyl, as complexing agent, in addition, is tested in the same manner as embodiment 33.Result is shown in table 9.
Embodiment 37
Use 2-aminomethyl-pyridine to replace 2,2 '-bipyridyl, as complexing agent, in addition, is tested in the same manner as embodiment 34.Result is shown in table 9.
Comparative example 7
Be not used as the sulfuric acid 2 of complexing agent, 2 '-bipyridyl aqueous solution, use silver nitrate aqueous solution to replace silver complex, in addition, test in the same manner as embodiment 32.Result is shown in table 9.
[table 9]
As shown in table 9, utilize the respond well of inorganic agent of the present invention degraded cyano compound.

Claims (10)

1. the biodegrading process of a chemical substance, it is characterized in that, it makes chemical substance degraded inorganic agent contact with chemical substance, described chemical substance contains cyanide and/or metal cyanide complex, described chemical substance degraded inorganic agent is the inorganic agent for chemical substance of degrading, and described chemical substance degraded inorganic agent contains (i) persulfate and silver complex, or containing (ii) persulfate, silver compound and complexing agent, described biodegrading process uses relative to the inorganic agent of the cyanide 1.0mgCN in described chemical substance at least containing 0.2g persulfate, make the temperature of the described chemical substance in process be up to 50 DEG C, described silver complex is selected from by 2,2 '-bipyridyl, 2-aminomethyl-pyridine, terpyridyl, pyridine carboxylic acid, 2-pyridine ethanol, 3-aminopyridine, 2-aminopyrimidine, 1,2-diaminopropanes, at least one in the group of 1,3-diaminopropanes and glycine composition is formed as complexing agent, or described complexing agent is for being selected from by 2,2 '-bipyridyl, 2-aminomethyl-pyridine, terpyridyl, pyridine carboxylic acid, 2-pyridine ethanol, 3-aminopyridine, 2-aminopyrimidine, 1,2-diaminopropanes, at least one in the group of 1,3-diaminopropanes and glycine composition.
2. biodegrading process according to claim 1, is characterized in that, the pH of the described chemical substance in process is remained on 4 ~ 11.
3. biodegrading process according to claim 1, is characterized in that, also adds pH adjusting agent.
4. biodegrading process according to claim 3, wherein, described pH adjusting agent is acetate type buffer.
5. biodegrading process according to claim 4, wherein, described acetate type buffer is acetic acid and/or sodium acetate.
6. biodegrading process according to claim 1, wherein, described chemical substance is the combination of one or more materials be selected from the group that is made up of soil, underground water, waste water and discarded object.
7. biodegrading process according to claim 1, is characterized in that, described inorganic agent and described chemical substance is uniformly mixed.
8. biodegrading process according to claim 1, wherein, described silver compound is be selected from least one in the group that is made up of silver nitrate, silver sulfate, silver nitrite, silver sulfite, silver carbonate, silver orthophosphate, boric acid silver, silver acetate, silver oxalate, silver citrate and silver oxide.
9. biodegrading process according to claim 1, wherein, described persulfate is peracetic dithionite.
10. biodegrading process according to claim 1, described chemical substance degraded inorganic agent is also containing sulfate.
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JP5873245B2 (en) * 2011-03-04 2016-03-01 新日鉄住金エンジニアリング株式会社 How to clean the contaminated area
JP5779115B2 (en) * 2012-02-06 2015-09-16 大成建設株式会社 Cyanide purification method
JP5194223B1 (en) * 2012-03-05 2013-05-08 株式会社セイネン Chemical treatment agent
CN103752601B (en) * 2013-12-31 2015-08-05 北京高能时代环境技术股份有限公司 A kind of method for orgnic compound pollution in rehabilitating soil and/or water
CN103965122B (en) * 2014-03-18 2016-03-30 浙江工业大学 A kind of nitrifying method of quinoxaline alkane substitute
JP6621234B2 (en) * 2014-09-01 2019-12-18 日鉄エンジニアリング株式会社 How to clean the contaminated area
CN104261506B (en) * 2014-09-19 2016-04-20 山东大学 The method of the formaldehyde in a kind of terpyridyl base gelatinous material process trade effluent
CN104438300B (en) * 2014-10-23 2017-01-18 江苏盖亚环境工程有限公司 Synergetic restoration method for gasoline contaminated soil
CN105344704B (en) * 2015-11-30 2019-02-26 重庆大学 A kind of method of petroleum hydrocarbon contaminated soil reparation
CN108530999B (en) * 2018-04-26 2020-09-01 云南大学 Conductive anticorrosive paint using organic silver as photocuring accelerator
CN111362449B (en) * 2020-02-19 2021-10-15 大连理工大学 Method for removing antibiotic resistance genes by activating persulfate through silver ammonia solution
KR102657465B1 (en) 2021-03-04 2024-04-16 (주) 테크윈 Stabilization method of persulfate solution

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0832852A2 (en) * 1996-09-30 1998-04-01 Peroxid-Chemie GmbH Process for degrading noxious substances
CN101549916A (en) * 2008-03-31 2009-10-07 李成心 Method for treating electroplating cyanide waste water

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1560450A (en) * 1968-01-16 1969-03-21
FR2219121A1 (en) * 1973-02-26 1974-09-20 Degremont Cyanide effluent purication - by successive absorption in cationic, weak anionic and strong anionic resin beds
JPS57180481A (en) * 1981-04-28 1982-11-06 Mitsubishi Heavy Ind Ltd Decomposing method for cyan of high concentration
JPH05345189A (en) * 1992-06-12 1993-12-27 Nippon Steel Corp Method for treating organic halogen compound-containing waste water
JP2002361269A (en) * 2001-06-06 2002-12-17 Nippon Gosei Alcohol Kk Method for treating water containing phosphorus
US20040197150A1 (en) * 2003-04-04 2004-10-07 Xpert Design And Diagnostics, Llc Chemical oxidation of organic and inorganic contaminants by chelated transition metals catalyzed persulfate
BRPI0506799A (en) * 2004-01-12 2007-05-22 Ciba Sc Holding Ag use of metal complex compounds comprising ligands derived from s-triazine or pyridine pyrimidine as catalysts for oxidation with organic peroxyacids and / or organic peroxyacid precursors and h2o2
PT1720802E (en) * 2004-02-26 2013-11-13 Fmc Corp Oxidation of organic compounds at high ph
JP2006326121A (en) * 2005-05-30 2006-12-07 Adeka Corp Chemical substance decomposition agent and cleaning method using thereof
US7794607B2 (en) * 2005-06-22 2010-09-14 Truox, Inc. Composition and method for enhanced sanitation and oxidation of aqueous systems
US7572390B2 (en) * 2005-06-22 2009-08-11 Truox, Inc. Composition and method for reducing chemical oxygen demand in water
US7695631B2 (en) * 2005-06-22 2010-04-13 Truox, Inc. Composition and method for reducing chemical oxygen demand in water
WO2007090461A1 (en) * 2006-02-06 2007-08-16 Ciba Holding Inc. Use of metal complex compounds as oxidation catalysts
WO2008065631A1 (en) * 2006-11-30 2008-06-05 Joanne Raphael Katz Method and composition for treating water
CN101172691A (en) * 2007-12-11 2008-05-07 大连海事大学 Method for processing sulphuric acid free radical oxidized water
JP5029562B2 (en) * 2008-10-02 2012-09-19 三菱瓦斯化学株式会社 Soil and / or groundwater purification method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0832852A2 (en) * 1996-09-30 1998-04-01 Peroxid-Chemie GmbH Process for degrading noxious substances
CN101549916A (en) * 2008-03-31 2009-10-07 李成心 Method for treating electroplating cyanide waste water

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
含氰废水的综合利用及其处理;娄性义等;《青岛建筑工程学院学报》;19870702(第2期);第39-46页 *

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