CN102883783A - Treatment agent for decomposition of chemical substance which comprises persulfuric acid salt and silver complex, and method for decomposition of chemical substance using same - Google Patents

Treatment agent for decomposition of chemical substance which comprises persulfuric acid salt and silver complex, and method for decomposition of chemical substance using same Download PDF

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Publication number
CN102883783A
CN102883783A CN2011800212917A CN201180021291A CN102883783A CN 102883783 A CN102883783 A CN 102883783A CN 2011800212917 A CN2011800212917 A CN 2011800212917A CN 201180021291 A CN201180021291 A CN 201180021291A CN 102883783 A CN102883783 A CN 102883783A
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silver
chemical substance
inorganic agent
cyanide
complex
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CN102883783B (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
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
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    • 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
    • C07D213/06—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
    • 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
    • C07D213/36—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
    • 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
    • C07D213/60—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
    • C—CHEMISTRY; METALLURGY
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    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • 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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  • Soil Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Processing Of Solid Wastes (AREA)
  • Removal Of Specific Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Disclosed are: a treatment agent for use in the decomposition of a chemical substance, which can decompose the chemical substance safely and with high efficiency and is economically advantageous; and a method for decomposing a chemical substance using the treatment agent. Specifically disclosed are: a treatment agent for use in the decomposition of a chemical substance, which is characterized by comprising a persulfuric acid salt and a silver complex; and a method for decomposing a chemical substance using the treatment agent.

Description

The chemical substance degraded that contains persulfate and silver complex is with inorganic agent and used the biodegrading process of its chemical substance
Technical field
The chemical substance degraded that the present invention relates to contain persulfate and silver complex is with inorganic agent and used the biodegrading process of its chemical substance.
Background technology
There was processing to be designated as the zone that needs zone to be processed, need to report when proterties changes as the soil great majority of the history of chemical substance, for example VOC, cyanide and/or the metal cyanide complex of the object of Japanese Soil Pollution Control method, consisted of social concern.In addition, cause the generation of oil pollution as the products from crude oil of the object of Japanese oil pollution guide, consist of living environment is produced dysgenic reason.For cyanide herein, for example can list the cyanide of the generation cyanide ion of hydrogen cyanide, Cymag and so on.In addition, for metal cyanide complex, for example can enumerate ion and the salt thereof of the cyano complex that taps a blast furnace, copper cyano complex.
For the processing method as the chemical substance of the object of Japanese Soil Pollution Control method or preventing and treating pollution of oil guide, can list in-situ oxidation edman degradation Edman, biological prosthetic, Powder by Iron Powder etc.The in-situ oxidation edman degradation Edman is the method that the catalyst combination such as persulfate, this oxidant of hydrogen peroxide and iron are purified, but the material of this refractory organics of hard degradation carrene.In addition, with bioanalysis, Powder by Iron Powder also this material of hard degradation carrene.
As the processing method of cyanogen, can list the methods such as chlor-alkali, acid volatilization absorption method, flocculent precipitation, hydro-thermal reaction method.
Chlor-alkali is following method: make the processing object be in the above alkaline state of pH10, then add the oxidants such as chlorine, hypochlorous acid, potassium permanganate and carry out oxidative degradation (referring to non-patent literature 1).Yet although the cyanide that the method can be degraded and be easier to degrade, hard degradation six cyanogen close the metal cyanide complex of the refractory organics of ferrous acid radical ion and so on.
Flocculent precipitation is the processing method (referring to non-patent literature 2) of cyanogen that can also be applied to process the metal cyanide complex of the refractory organics that is difficult to oxidative degradation.For example, by in the waste water that contains six cyanogen and close the ferrous acid radical ion, adding excessive iron ion, copper ion or zinc ion, can generate insoluble six cyanogen close ferrous acid heavy metallic salt precipitation and from waste water, separate and remove.Yet, because this facture is to make cyanogen form that infusible precipitate separates but not the technology of degrade, so can't be applied to the original position method of purification of soil.
Acid volatilization absorption method is by making the processing object be in the method that the acid state below the pH3 generates hydrogen cyanide and removes with the gas form volatilization.Yet, owing to hydrogen cyanide is widely known by the people as severe toxicity, so security existing problems, existing problems when particularly in position soil and/or underground water being processed.In addition, thus also have secondary pollution by making soil be acidity below the pH3 heavy metal composition stripping in the soil to be produced caused by heavy metal, the anxiety of the corrosion of reinforcing bar, underground piping as underground structure occurs.
The hydro-thermal reaction method be by add depress, more than 150 ℃ to metal cyanide complex process the to degrade technology (referring to patent documentation 1) of cyanogen.Yet this facture need to move to the processing object in the pressure vessel and process, and therefore is difficult to be applied to original position and purifies.
With respect to these, disclose in the patent documentation 2 by with the high temperature more than 80 ℃ the object that contains metal cyanide complex being carried out the degrade method of cyanogen of oxidation processes.Yet, be difficult to a large amount of soil and/or underground water are heated to high temperature in position and keep in economy, therefore be difficult to be applied to original position and purify.
Disclose in the patent documentation 3 with the ozone with high oxidation power and will contain the method for the cyanogen degraded in the object of metal cyanide complex.Yet, use poisonous ozone not only to exist and can produce to the ecosystem anxiety of harmful effect, and need residual ozone is carried out degradation treatment after processing, therefore have the heavy shortcoming of facility load.
Also biodegradation method is attempted, but had the shortcoming that is difficult to be applied to contain with high concentration the pollution of the virose cyanogen of tool.
In addition, disclose in the patent documentation 4 when remaining on conversion zone more than the pH5 add in the scope at 100 ~ 1000mg/L persulfate with by chemical contamination the method for pollutant purification.Yet, although the purification of being undertaken by the interpolation persulfate is effectively for chemical substances such as organochlorine compounds, the metal cyanide complex of hard degradation refractory organics.
The prior art document
Patent documentation
Patent documentation 1: Japanese Patent Publication 55-50718 communique
Patent documentation 2: Japanese kokai publication sho 50-118962 communique
Patent documentation 3: TOHKEMY 2000-153284 communique
Patent documentation 4: No. 4027209 communiques of Japan's special permission
Non-patent literature
Non-patent literature 1: plating technical manual revised edition (め つ き Ji Intraoperative ガ イ De changes the Order version), Japanese gilding synergistic combination, 2004,496 pages
Non-patent literature 2: plating technical manual revised edition (め つ き Ji Intraoperative ガ イ De changes the 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 variety of issue of above-mentioned this prior art, safety is provided and degrade efficiently chemical substance and also economically useful chemical substance degraded with inorganic agent and the biodegrading process that used its chemical substance.
For the scheme of dealing with problems
The inventor etc. conduct in-depth research in order to address the above problem, and found that, contain the inorganic agent of persulfate and silver complex by use, the chemical substance of refractory organics of can easily degrading, thus finished the present invention.
That is, above-mentioned problem can solve by following the present invention.
＜1〉an embodiment of the invention are that inorganic agent is used in a kind of chemical substance degraded, it is characterized in that it contains persulfate and silver complex for being used for the inorganic agent of degraded chemical substance.
＜2〉optimal way of the present invention is above-mentioned＜1〉described inorganic agent, it is characterized in that aforementioned silver complex is selected from least a in the group that is comprised of the compound that contains pyridine ring, the compound that contains pyrimidine ring, the compound that contains the ethylenediamine structure, hydroxycarboxylic acid, amino acids and diaminopropanes and forms as complexing agent.
＜3〉another optimal way of the present invention is above-mentioned＜2〉described inorganic agent, it is characterized in that, aforementioned silver complex is to be 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, 1,2-diaminopropanes, 1, at least a in the group that 3-diaminopropanes and glycine form forms as complexing agent.
＜4〉another embodiment of the present invention is that inorganic agent is used in a kind of chemical substance degraded, it is characterized in that it contains persulfate, silver compound and complexing agent for being used for the inorganic agent of degraded chemical substance.
＜5〉optimal way of the present invention is above-mentioned＜4〉described inorganic agent, wherein, aforementioned 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, ethylenediamine, tetramethylethylenediamine, ethylenediamine tetra-acetic acid, lactic acid, glycolic, 1,2-diaminopropanes, 1, at least a in the group that 3-diaminopropanes and glycine form.
＜6〉optimal way of the present invention is above-mentioned＜4〉or＜5〉described inorganic agent, wherein, aforementioned silver compound is to be selected from least a in the group that is comprised 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 optimal way of the present invention is above-mentioned＜1〉~＜6 in each described inorganic agent, wherein, aforementioned persulfate is peracetic dithionite.
＜8〉another optimal way of the present invention is above-mentioned＜1〉~＜7 in each described inorganic agent, it also contains sulfate.
＜9〉another optimal way of the present invention is above-mentioned＜1〉~＜8 in each described inorganic agent, wherein, aforementioned chemical substance 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 above-mentioned＜1〉~＜8 in each described inorganic agent contact with chemical substance, described chemical substance contains at least a in VOC, products from crude oil, cyanide or the metal cyanide complex.
＜11〉optimal way of the present invention is above-mentioned＜10〉described biodegrading process, it is characterized in that, the pH of the aforementioned chemical substance in processing is remained on 4 ~ 11.
＜12〉another optimal way of the present invention is above-mentioned＜10〉or＜11〉described biodegrading process, it is characterized in that, also add pH adjusting agent.
＜13〉another optimal way of the present invention is above-mentioned＜12〉described biodegrading process, wherein, aforementioned pH adjusting agent is the acetate type buffer.
＜14〉another optimal way of the present invention is above-mentioned＜13〉described biodegrading process, wherein, aforementioned acetate type buffer is acetic acid and/or sodium acetate.
＜15〉another optimal way of the present invention is above-mentioned＜10〉~＜14 in each described biodegrading process, it is characterized in that, make the temperature of the aforementioned chemical substance in the processing be up to 70 ℃.
＜16〉another optimal way of the present invention is above-mentioned＜10〉~＜15 in each described biodegrading process, wherein, aforementioned chemical substance is the combination that is selected from one or more materials in the group that is comprised of soil, underground water, waste water and discarded object.
＜17〉another optimal way of the present invention is above-mentioned＜10〉~＜16 in each described biodegrading process, it is characterized in that, when aforementioned chemical substance contains cyanide and/or metal cyanide complex, use the inorganic agent that contains at least the 0.1g persulfate with respect to the cyanide 1.0mgCN in the aforementioned chemical substance.
＜18〉another optimal way of the present invention is above-mentioned＜10〉~＜17 in each described biodegrading process, it is characterized in that, aforementioned processing agent and aforementioned chemical substance are mixed.
The effect of invention
With inorganic agent and used the biodegrading process of its chemical substance, has following effect according to the degraded of the chemical substance of optimal way of the present invention.
(1) has high oxidizing force, the chemical substance such as the cyanide that is difficult to oxidative degradation of can securely and effectively degrading, metal cyanide complex, carrene.
(2) will remain on as the pH of the chemical substance of object neutral near in degraded cyanogen, so the cyanide of can degrading, metal cyanide complex and do not produce hydrogen cyanide and not stripping heavy metal composition.
(3) be in the situation of the polluted soil such as cyanide, metal cyanide complex and/or underground water in the chemical substance that is used as object, can carry out in position oxidative degradation.
Therefore, according to the present invention, the chemical substances such as the cyanide of the formation pollution cause of can securely and effectively degrading, metal cyanide complex.
The specific embodiment
Below describe the present invention in detail.
An embodiment of the invention are that inorganic agent is used in a kind of chemical substance degraded, it is characterized in that it contains persulfate and silver complex for being used for the inorganic agent of degraded chemical substance.Replacing above-mentioned silver complex, also can be the material that contains silver compound and complexing agent and form silver complex when using inorganic agent.
Chemical substance of the present invention is the chemical substance that consists of the pollution cause of soil, underground water, waste water and discarded object etc., is the material of stipulating in the Japanese Soil Pollution Control methods such as VOC, cyanide, metal cyanide complex; The products from crude oil of being stipulated by guide because of oil film oil gas flavor.Cyanide of the present invention refers to have by dissociating the compound of cyanide ion.As cyanide, such as listing hydrogen cyanide, Cymag, potassium cyanide etc.Metal cyanide complex refers to produce by dissociating the complex compound of cyanide ion, cyanide or hydrogen cyanide and the salt of complex compound.Close ferrous acid radical ion, Hexacyanoferrate radical ion, five 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 nitrosyl ferrous acid radical ion such as listing six cyanogen.As VOC of the present invention, for example can list 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, such as listing light oil, kerosene, gasoline, heavy oil etc.
Inorganic agent of the present invention can be applied to contain the object of chemical substance.As object, can list the solid, liquid or the slurries that contain chemical substance.Object can contain gas in its part.For example can list one or more the combination that is selected from soil, underground water, waste water and the discarded object, but be not limited to these 4 kinds.
Persulfate in the inorganic agent of the present invention is not particularly limited, such as using sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate etc.From the size of the solubility water, preferred sodium peroxydisulfate and ammonium persulfate never exist by ammonia nitrogen to cause the anxiety of secondary pollution to be set out, 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, can uses the aqueous solution, suspension, powder, aerosol etc.Can the consumption of persulfate can be to purify object as index by the test of purification property, select suitable amount according to the content of the chemical substance in the object, and when chemical substance is cyanide, preferably be at least 0.1g with respect to the cyanide 1.0mgCN in the object, more preferably more than the 0.2g, most preferably be more than the 0.5g.Consider economy and the variation that slows down the pH of object, the upper limit of the consumption of persulfate is below the 50g with respect to the 1kg object preferably, more preferably below the 20g, most preferably is below the 10g.Herein, cyanide amount total cyanogen concentration that can be recorded by " the total cyanogen of 38.1.2 (the Total Cyanogen) " and " 38.34-pyridine carboxylic acid-pyrazolone absorption photometry (Pyridinecarboxylic Acid-PyrazoloneAbsorptiometry) " of foundation JIS K0102:2008 and obtaining.
The complexing agent that is used to form silver complex of the present invention is not particularly limited, is preferably selected from the compound in the compound that contains pyridine ring, the compound that contains pyrimidine ring, the compound that contains the ethylenediamine structure, hydroxycarboxylic acid, amino acids and the diaminopropanes.
As the compound that contains pyridine ring, for example can list 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 that contains pyrimidine ring, for example can list 2-aminopyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4,6-dimethyl pyrimidine, 2,4-dimethylamino yl pyrimidines etc.
As the compound that contains the ethylenediamine structure, for example can list 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, such as listing lactic acid, malic acid, glycolic, tartaric acid, citric acid, gluconic acid, grape saccharic acid etc.
As amino acids, for example can list glycine, alanine, aspartic acid, NTA, 1,3-trimethylen-edinitrilo-tetraacetic acid etc.
Complexing agent of the present invention more preferably 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, in 3-diaminopropanes and the glycine more than one, be particularly preferably 2,2 '-bipyridyl.
In addition, as long as the silver compound that uses in the silver complex can form silver complex with above-mentioned complexing agent and then be not particularly limited, such as listing 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, be suitably silver nitrate, silver sulfate, silver acetate and silver oxide.Silver compound in the silver complex of the present invention then is not particularly limited in the scope of not damaging effect of the present invention than needing only with the compounding of complexing agent, as the mol ratio (complexing agent/silver ion) of complexing agent with respect to silver compound (by silver ion), be preferably 0.2 ~ 3, 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 then can produce the precipitation of silver salt and not preferred.
The form of adding silver complex is not particularly limited, can uses the aqueous solution, suspension, powder, aerosol etc.Can the consumption of silver complex can be to purify object as index by the test of purification property, select suitable amount according to the content of the chemical substance in the object, when chemical substance is cyanide, preferably be at least 0.1mgAg with respect to the cyanide 1.0mgCN in the object, more preferably more than the 0.5mgAg, most preferably be more than the 1.0mgAg.Consider economy, the upper limit of the consumption of silver complex is below the 100mgAg with respect to the 1kg object preferably, more preferably below the 40mgAg, most preferably is below the 10mgAg.
Inorganic agent of the present invention contains persulfate and silver complex, or contains persulfate and silver compound and complexing agent, and persulfate and silver complex (perhaps silver compound and complexing agent) can be pre-mixed, and also can mix before being about to use.In addition, also the aqueous solution that contains separately respectively them can be mixed before being about to use.
To the sulfate that uses among the present invention without limits, in order to reduce the kind that is discharged into the material in the environment as far as possible, it is identical with employed persulfate to it is desirable to cation type.For example, during as cleanser, preferably selected sodium sulphate is as sulfate at selected sodium peroxydisulfate.With respect to persulfate 100 weight portions, the sulfate amount of using 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 can't be promoted the effect of degradation of pollutant, even and therefore the effect of the degree that excessive supply also can't obtain expecting is not preferred economically.
In the present invention, can be by above-mentioned inorganic agent be contacted degrade the chemical substance in the object with the object that contains chemical substance.In order to make above-mentioned inorganic agent and object high-efficient contact promote degraded, it also is effective that inorganic agent and object are mixed by force.In addition, when the chemical substance concentration of object is high, also above-mentioned inorganic agent can be repeated to add in the object and process.
In cyanide in object and/or the degraded of metal cyanide complex, the pH of the object in preferably will processing remains on 4 ~ 11.If then there are the anxiety that produces hydrogen cyanide in degraded cyanide and/or metal cyanide complex under the low state of the pH of object, generate the anxiety that insoluble silver oxide precipitates, the cyanogen degraded is incomplete in the next existence of the high state of pH.And then, from the angle of environmental protection, the preferably time enforcement in pH4 ~ 9.
At the pH of object along with the carrying out of the interpolation of medicament, degraded and when changing, for the pH with object remains on 4 ~ 11, can use pH adjusting agent.Among the present invention, owing to use the inorganic agent that contains persulfate, the pH of object can reduce along with the carrying out of degraded sometimes, therefore the suitable pH adjusting agent of adding.PH adjusting agent is not particularly limited, can uses the combination of alkali compounds and/or alkali compounds and acid compound, can preferably use the compound group that is called as the pH buffer.As the pH buffer, can list lemon acids, phosphoric acid class, boric acid class, carbonic acid class, acetate type buffer etc., wherein, preferred acetate type buffer.As the acetate type buffer, can use lithium acetate, sodium acetate, potassium acetate, calcium acetate, magnesium acetate etc.Wherein, from the angle of economy, preferably use sodium acetate and/or acetic acid.Sodium acetate can use any in trihydrate, the anhydride.
In the degraded of the chemical substance of utilizing inorganic agent of the present invention to carry out, even the heating target thing chemical substance of also can degrading efficiently not.Therefore, if use inorganic agent of the present invention, then do not need the auxiliary device for the heating target thing, and can be used for aptly the original position purification of soil and/or underground water, therefore industrial highly beneficial.When needs carry out degradation treatment rapidly, also can the heating target thing, and viewpoint dangerous from the operation that is brought by the operation thermal source, economy, further contemplate when object is cyanide and/or metal cyanide complex and to have the anxiety etc. that produces hydrogen cyanide because of heating, the temperature of object is up to 70 ℃, more preferably below 50 ℃.
The biodegrading process of chemical substance of the present invention can be used for soil and/or underground water purification in position aptly.The method of adding above-mentioned inorganic agent and pH adjusting agent in subtend soil and/or the underground water is not particularly limited, and can use injections, be pressed into, sprays, stirs, naturally spreads, permeates, adds to the injected system of drawing water etc.In addition, also can be by aspirate, reduce pressure to control speed, the direction of interpolation in the position that is different from point of addition.
Embodiment
The below illustrates embodiment and further specifically describes the present invention.But the present invention also is not limited by the following examples.In addition, the concentration of persulfate is obtained by permanganimetric method.
Embodiment 1
Dissolving six cyanogen close ferrous acid potassium (little the special grade chemical that chemicals Co., Ltd. makes) in pure water, and preparation concentration is the simulating pollution water of 10mgCN/L.Will be as 2 of complexing agent, 2 '-bipyridyl (special grade chemical that Wako Pure Chemical Industries, Ltd. makes) is dissolved in the aqueous sulfuric acid, prepares 0.16 % by weight sulfuric acid 2,2 '-bipyridyl aqueous solution.To be dissolved in as the silver nitrate (little the special grade chemical that chemicals Co., Ltd. makes) of silver compound and prepare silver nitrate aqueous solution in the pure water, mix above-mentioned sulfuric acid 2,2 '-bipyridyl aqueous solution, preparation is as the silver-2 of silver complex, 2 '-bipyridyl complexes aqueous solution.In glass sample preparation QC, add 50.0g simulating pollution water, with 1.36g as the sodium acetate trihydrate of pH adjusting agent (special grade chemical that little ancestor's chemicals Co., Ltd. makes) with as after the sodium peroxydisulfate of persulfate (sodium peroxydisulfate, one-level reagent that the little ancestor's chemicals Co., Ltd. makes) dissolving, mix above-mentioned silver-2,2 '-bipyridyl complexes aqueous solution, at room temperature, the dark place left standstill 6 days.Measure persulfate concentration and the total cyanogen concentration that leaves standstill front and back by following method.The results are shown in table 1.
The mensuration of＜persulfate concentration 〉
Calculated the residual rate of persulfate by the persulfate concentration before and after leaving standstill.Persulfate concentration is measured by the back titration of the following stated.
(1) gets the ferrous aqueous solution of ammonium sulfate to beaker, add in right amount after the aqueous sulfuric acid, use the potassium permanganate solution titration, thereby measure the concentration of the ferrous aqueous solution of ammonium sulfate.
(2) get the ferrous aqueous solution of ammonium sulfate and contain the sample of persulfate to beaker.At this moment, getting with respect to persulfate is excessive ammonium sulfate ferrous iron.
(3) add in right amount aqueous sulfuric acid.
(4) use the potassium permanganate solution titration.
The mensuration of＜total cyanogen concentration 〉
Total cyanogen concentration before and after mensuration leaves standstill.Total cyanogen concentration is measured with following methods.When containing precipitation in the treatment fluid after leaving standstill, the total cyanogen concentration of value conduct that will measure divided by treatment fluid with the summation of the total cyanogen amount that contains in precipitation and the supernatant.
(1) sample is taken in the beaker, dilutes with pure water as required.
(2) ascorbic acid of 10 times of equivalents of the persulfate that contains in the sample form with 10 % by weight aqueous ascorbic acids is added, remove persulfate.
(3) for the total cyanogen concentration that contains in the sample of having removed persulfate, measure according to JIS K0102:2008 " the total cyanogen of 38.1.2 " and " 38.34-pyridine carboxylic acid-pyrazolone absorption photometry ".In addition, in aforementioned mensuration according to JIS, total cyanogen concentration quantitatively be limited to 0.1mgCN/L.
Embodiment 2 ~ 4
As complexing agent, use 2-aminomethyl-pyridine (reagent that Tokyo HuaCheng Industry Co., Ltd makes), ethylenediamine (special grade chemical that Wako Pure Chemical Industries, Ltd. makes) or tetramethylethylenediamine (reagent that Sigma-Aldrich Co.LLC. makes) 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 the silver-2 as silver complex, in addition 2 '-bipyridyl complexes aqueous solution, test similarly to Example 1.The results are shown in table 1.
Comparative example 2
Do not use the sulfuric acid 2 as complexing agent, 2 '-bipyridyl aqueous solution replaces silver complex and silver nitrate aqueous solution is mixed in the contaminant water, in addition, tests similarly to Example 1.The results are shown in table 1.
[table 1]
As shown in table 1, be used as inorganic agent of the present invention by adding persulfate and silver compound with the complexing agent that contains pyridine ring or ethylenediamine structure, promoted the degraded of cyanide.Especially, in the use 2 of embodiment 1,2 '-bipyridyl is during as complexing agent, the demonstration cyanide of can effectively degrading.
Comparative example 3 ~ 4
Mix FeSO4?7H2O (special grade chemical that Wako Pure Chemical Industries, Ltd. makes) and sulfuric acid 2,2 '-bipyridyl aqueous solution, the preparation iron complex aqueous solution.In addition, mix potassium permanganate (the rigorous analysis reagent that Wako Pure Chemical Industries, Ltd. makes) and sulfuric acid 2,2 '-bipyridyl aqueous solution, the preparation 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, making time of repose is 5 days, in addition, tests similarly to Example 1.The results are shown in table 2.
[table 2]
Figure BDA00002317000500141
As shown in Table 2, when having added persulfate and iron complex or persulfate and manganese complex, the cyanide of substantially can't degrading.
Embodiment 5 ~ 7
As pH adjusting agent, use citrate trisodium dihydrate (little the special grade chemical that chemicals Co., Ltd. makes), disodium hydrogen phosphate dihydrate or sodium acid carbonate (little the special grade chemical that chemicals Co., Ltd. makes) to replace the sodium acetate trihydrate, making time of repose is 2 days, 6 days or 4 days, in addition, test similarly to Example 1.The results are shown in table 3.
[table 3]
As shown in table 3, can use acetate type, lemon acids, phosphoric acid class and carbonic acid class buffer as pH adjusting agent in the biodegrading process of the present invention.Especially, using sodium acetate as the embodiment 1 of pH adjusting agent and using among the embodiment 7 of sodium acid carbonate as 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.The results are shown in table 4.
Embodiment 10 ~ 11
Change the addition of concentration, sodium peroxydisulfate, silver complex and the pH adjusting agent of simulating pollution water, in addition, test similarly to Example 1.The results are shown in table 4.
[table 4]
Figure BDA00002317000500161
As shown in table 4, in the system that silver complex is set as with respect to the consumption of 1.0mgCN cyanide more than the 0.2mgAg, the degraded of cyanide has obtained promotion.When silver complex is set as 1.0mgAg with respect to the consumption of 1.0mgCN cyanide, leave standstill 6 days after, with cyanide degradation to the total cyanogen concentration that meets environmental standard (the relevant environment standard of soil pollution) less than 0.1mgCN/L.
Embodiment 12 ~ 14
In addition change, tests similarly to Example 1 as the addition of the sodium peroxydisulfate of persulfate with as the addition of the sodium acetate trihydrate of pH adjusting agent.The results are shown in table 5.
[table 5]
Figure BDA00002317000500171
As shown in table 5, in the system that persulfate is set as with respect to the consumption of 1.0mgCN cyanide more than the 0.2g, the degraded of cyanide has obtained promotion.After persulfate being set as 0.5g when above with respect to the consumption of 1.0mgCN cyanide, leaving standstill 6 days, with cyanide degradation to the total cyanogen concentration that meets environmental standard (the relevant environment standard of soil pollution) less than 0.1mgCN/L.
Embodiment 15 ~ 17
When the preparation silver complex aqueous solution, change as the silver nitrate aqueous solution of silver compound with as the sulfuric acid 2 of complexing agent, in addition the concentration of 2 '-bipyridyl aqueous solution, test similarly to Example 1.The results are shown in table 6.
[table 6]
Figure BDA00002317000500181
As shown in table 6, when the mol ratio with complexing agent/silver ion is set as more than 0.5 times, leave standstill 6 days after, with cyanide degradation to the total cyanogen concentration that meets environmental standard (the relevant environment standard of soil pollution) less than 0.1mgCN/L.
Embodiment 18
As persulfate, use ammonium persulfate (special grade chemical that Kanto Kagaku K. K. makes) to replace sodium peroxydisulfate, in addition, test similarly to Example 13.The results are shown in table 7.
[table 7]
Figure BDA00002317000500182
As shown in table 7, when using ammonium persulfate as inorganic agent of the present invention, same with the situation of using sodium peroxydisulfate, the degradation effect of cyanide is good.
Embodiment 19
Dissolve carrene (little the special grade chemical that chemicals Co., Ltd. makes) in pure water, preparation concentration is the simulating pollution water of 19mg/L.Will be as 2 of complexing agent, 2 '-bipyridyl (special grade chemical that Wako Pure Chemical Industries, Ltd. makes) is dissolved in the aqueous sulfuric acid, prepares 0.16 % by weight sulfuric acid 2,2 '-bipyridyl aqueous solution.To be dissolved in as the silver nitrate (little the special grade chemical that chemicals Co., Ltd. makes) of silver compound and prepare silver nitrate aqueous solution in the pure water, mix above-mentioned sulfuric acid 2,2 '-bipyridyl aqueous solution, preparation is as the silver-2 of silver complex, 2 '-bipyridyl complexes aqueous solution.
At the withstand voltage screw socket bottle (volume that does not contain stirrer: 131mL) of glass system, adding as the sodium acid carbonate of pH adjusting agent (special grade chemical that the little ancestor's chemicals Co., Ltd. makes) aqueous solution so that it reaches 0.1M, in dissolving as the sodium peroxydisulfate of persulfate (sodium peroxydisulfate, one-level reagent that little ancestor's chemicals Co., Ltd. makes) afterwards, the 100mL simulating pollution water of packing into, 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 stirred 2 days.Persulfate concentration and concentration dichloromethane before and after mensuration leaves standstill.Concentration dichloromethane is passed through Headspace Gas Chromatography.The results are 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 the table 8 to replace 2, in addition 2 '-bipyridyl, tests similarly to Example 19.The results are shown in table 8.
Comparative example 5
Do not use the silver-2 as silver complex, in addition 2 '-bipyridyl complexes aqueous solution, test similarly to Example 19.The results are shown in table 8.
Comparative example 6
Do not use the silver-2 as silver complex, 2 '-bipyridyl complexes aqueous solution, in addition the use silver nitrate aqueous solution that replaces, tests similarly to Example 19.The results are shown in table 8.
[table 8]
Figure BDA00002317000500201
As shown in table 8, when having used the inorganic agent that contains sodium peroxydisulfate and silver complex of the present invention, the degradation effect of carrene is good.
Embodiment 32
As pH adjusting agent, dissolving 3.40g sodium acetate trihydrate replaces dissolving 1.36g sodium acetate trihydrate, time of repose is set as replace 6 days over 2 days, in addition, tests similarly to Example 1.The results are shown in table 9.
Embodiment 33
Replacement dissolving as the sodium acetate trihydrate of pH adjusting agent and as the sodium peroxydisulfate of persulfate after mixing as the silver-2 of silver complex, the operation of 2 '-bipyridyl complexes aqueous solution, change dissolving sodium acetate trihydrate into, then combined silver-2,2 '-bipyridyl complexes aqueous solution, further in addition the dissolving sodium peroxydisulfate, similarly tests with embodiment 32.The results are shown in table 9.
Embodiment 34
Dissolving six cyanogen close ferrous acid potassium in pure water, and preparation concentration is the simulating pollution water of 20mgCN/L.Will be as 2 of complexing agent, 2 '-bipyridyl is dissolved in the aqueous sulfuric acid, prepares 0.16 % by weight sulfuric acid 2,2 '-bipyridyl aqueous solution.To be dissolved in the pure water as the silver nitrate of silver compound and prepare silver nitrate aqueous solution, mix above-mentioned sulfuric acid 2,2 '-bipyridyl aqueous solution, preparation is as the silver-2 of silver complex, 2 '-bipyridyl complexes aqueous solution.The 25.0g simulating pollution water of packing in glass sample preparation QC, dissolving 1.36g is as the sodium acetate trihydrate of pH adjusting agent (special grade chemical that little ancestor's chemicals Co., Ltd. makes).To be dissolved in mixing above-mentioned silver-2 in the sodium persulfate aqueous solution that forms in the 25.0g pure water as the sodium peroxydisulfate (little sodium peroxydisulfate, the one-level reagent that chemicals Co., Ltd. makes) of persulfate, then 2 '-bipyridyl complexes aqueous solution be mixed into total amount rapidly in the simulating pollution water that is dissolved with the sodium acetate trihydrate.At room temperature, left standstill 2 days the dark place.Measure persulfate concentration and the total cyanogen concentration that leaves standstill front and back by said method.The results are shown in table 9.
Embodiment 35
Use the 2-aminomethyl-pyridine to replace 2, in addition 2 '-bipyridyl, similarly tests with embodiment 32 as complexing agent.The results are shown in table 9.
Embodiment 36
Use the 2-aminomethyl-pyridine to replace 2, in addition 2 '-bipyridyl, similarly tests with embodiment 33 as complexing agent.The results are shown in table 9.
Embodiment 37
Use the 2-aminomethyl-pyridine to replace 2, in addition 2 '-bipyridyl, similarly tests with embodiment 34 as complexing agent.The results are shown in table 9.
Comparative example 7
Do not use the sulfuric acid 2 as complexing agent, 2 '-bipyridyl aqueous solution uses silver nitrate aqueous solution to replace silver complex, in addition, similarly tests with embodiment 32.The results are shown in table 9.
[table 9]
Figure BDA00002317000500221
As shown in table 9, utilize the respond well of inorganic agent degraded cyano compound of the present invention.

Claims (18)

1. inorganic agent is used in a chemical substance degraded, it is characterized in that it contains persulfate and silver complex for being used for the inorganic agent of degraded chemical substance.
2. inorganic agent according to claim 1, it is characterized in that described silver complex is selected from least a in the group that is comprised of the compound that contains pyridine ring, the compound that contains pyrimidine ring, the compound that contains the ethylenediamine structure, hydroxycarboxylic acid, amino acids and diaminopropanes and forms as complexing agent.
3. inorganic agent according to claim 2, it is characterized in that, described silver complex is to be 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, 1,2-diaminopropanes, 1, at least a in the group that 3-diaminopropanes and glycine form forms as complexing agent.
4. inorganic agent is used in a chemical substance degraded, it is characterized in that it contains persulfate, silver compound and complexing agent for being used for the inorganic agent of degraded chemical substance.
5. inorganic agent according to claim 4, wherein, 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, ethylenediamine, tetramethylethylenediamine, ethylenediamine tetra-acetic acid, lactic acid, glycolic, 1,2-diaminopropanes, 1, at least a in the group that 3-diaminopropanes and glycine form.
6. according to claim 4 or 5 described inorganic agents, wherein, described silver compound is to be selected from least a in the group that is comprised 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. each described inorganic agent according to claim 1 ~ 6, wherein, described persulfate is peracetic dithionite.
8. each described inorganic agent according to claim 1 ~ 7, it also contains sulfate.
9. each described inorganic agent according to claim 1 ~ 8, wherein, described chemical substance is cyanide and/or metal cyanide complex.
10. the biodegrading process of a chemical substance, it is characterized in that, it makes, and each described inorganic agent contacts with chemical substance in the claim 1 ~ 8, and described chemical substance contains at least a in VOC, products from crude oil, cyanide or the metal cyanide complex.
11. biodegrading process according to claim 10 is characterized in that, the pH of the described chemical substance in processing is remained on 4 ~ 11.
12. according to claim 10 or 11 described biodegrading process, it is characterized in that, also add pH adjusting agent.
13. biodegrading process according to claim 12, wherein, described pH adjusting agent is the acetate type buffer.
14. biodegrading process according to claim 13, wherein, described acetate type buffer is acetic acid and/or sodium acetate.
15. each described biodegrading process is characterized in that according to claim 10 ~ 14, makes the temperature of the described chemical substance in the processing be up to 70 ℃.
16. each described biodegrading process according to claim 10 ~ 15, wherein, described chemical substance is the combination that is selected from one or more materials in the group that is comprised of soil, underground water, waste water and discarded object.
17. each described biodegrading process according to claim 10 ~ 16, it is characterized in that, when described chemical substance contains cyanide and/or metal cyanide complex, use the inorganic agent that contains at least the 0.1g persulfate with respect to the cyanide 1.0mgCN in the described chemical substance.
18. each described biodegrading process is characterized in that according to claim 10 ~ 17, and described inorganic agent and described chemical substance are mixed.
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