JP7267112B2 - Method for remediation of contaminated soil - Google Patents
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- JP7267112B2 JP7267112B2 JP2019104415A JP2019104415A JP7267112B2 JP 7267112 B2 JP7267112 B2 JP 7267112B2 JP 2019104415 A JP2019104415 A JP 2019104415A JP 2019104415 A JP2019104415 A JP 2019104415A JP 7267112 B2 JP7267112 B2 JP 7267112B2
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- 239000002689 soil Substances 0.000 title claims description 175
- 238000000034 method Methods 0.000 title claims description 97
- 238000005067 remediation Methods 0.000 title claims description 30
- 239000007788 liquid Substances 0.000 claims description 69
- 238000002156 mixing Methods 0.000 claims description 60
- 238000006864 oxidative decomposition reaction Methods 0.000 claims description 50
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 48
- 239000000295 fuel oil Substances 0.000 claims description 31
- 239000012028 Fenton's reagent Substances 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 23
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 description 53
- 235000019198 oils Nutrition 0.000 description 53
- 238000000746 purification Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000006228 supernatant Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- -1 polycyclic aromatic compounds Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 150000004688 heptahydrates Chemical class 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229910000358 iron sulfate Inorganic materials 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- SCVOEYLBXCPATR-UHFFFAOYSA-L manganese(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Mn+2].[O-]S([O-])(=O)=O SCVOEYLBXCPATR-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 1
- JIPBPJZISZCBJQ-UHFFFAOYSA-N 1-[(2-methylpropan-2-yl)oxycarbonyl]-3-(pyridin-4-ylmethyl)piperidine-3-carboxylic acid Chemical compound C1N(C(=O)OC(C)(C)C)CCCC1(C(O)=O)CC1=CC=NC=C1 JIPBPJZISZCBJQ-UHFFFAOYSA-N 0.000 description 1
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 1
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 1
- 239000004343 Calcium peroxide Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 235000019774 Rice Bran oil Nutrition 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- CKFMJXZQTNRXGX-UHFFFAOYSA-L iron(2+);diperchlorate Chemical compound [Fe+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O CKFMJXZQTNRXGX-UHFFFAOYSA-L 0.000 description 1
- HQPMOXUTKURVDV-UHFFFAOYSA-L iron(2+);sulfate;pentahydrate Chemical compound O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O HQPMOXUTKURVDV-UHFFFAOYSA-L 0.000 description 1
- UQKCYIJPXBSQGJ-UHFFFAOYSA-L iron(2+);sulfate;tetrahydrate Chemical compound O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O UQKCYIJPXBSQGJ-UHFFFAOYSA-L 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 1
- CDUFCUKTJFSWPL-UHFFFAOYSA-L manganese(II) sulfate tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-]S([O-])(=O)=O CDUFCUKTJFSWPL-UHFFFAOYSA-L 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
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Description
本発明は、汚染土壌の浄化方法に関する。 The present invention relates to a method for remediation of contaminated soil.
従来から、油類や多環芳香族化合物などの特定有害物質で汚染された汚染土壌に薬剤を添加し、化学的に前記特定有害物質の分解を行う方法の１つとして、フェントン工法が提案されている（例えば、特許文献１参照）。 Conventionally, the Fenton method has been proposed as one method of chemically decomposing the specified hazardous substances by adding chemicals to contaminated soil contaminated with specified hazardous substances such as oils and polycyclic aromatic compounds. (See, for example, Patent Document 1).
しかし、前記フェントン工法は、揮発性有機化合物や低炭素数であるガソリンなどの油種には効果があるが、重油や絶縁油などへの効果は低いという問題がある。 However, although the Fenton method is effective for oil types such as volatile organic compounds and gasoline with a low carbon number, there is a problem that the effect is low for heavy oil and insulating oil.
本発明は、ガソリン、重油、絶縁油などの低～高炭素数の油類により汚染された汚染土壌を、現場において効率良く浄化することができる汚染土壌の浄化方法を提供することを目的とする。 An object of the present invention is to provide a method for remediation of contaminated soil that can efficiently remediate contaminated soil contaminated with low to high carbon number oils such as gasoline, heavy oil, and insulating oil on site. .
前記課題を解決するための手段としては、以下の通りである。即ち、
＜１＞ 重油により汚染された汚染土壌に対して液体を添加し、前記汚染土壌と前記液体を混合する混合工程と、
前記汚染土壌から前記液体を除去する液体除去工程と、
前記液体除去工程の後に、前記汚染土壌に対して過酸化水素及び触媒を含有するフェントン試薬を添加し、前記汚染土壌中の炭化水素化合物を酸化分解する酸化分解工程と、
を含み、前記酸化分解工程を２回以上行い、
前記過酸化水素を、前記汚染土壌に対して０．０１ｍｏｌ／ｋｇ以上０．１ｍｏｌ／ｋｇ以下添加することを特徴とする汚染土壌の浄化方法である。
＜２＞ 前記酸化分解工程において、前記汚染土壌に対して、過酸化水素及び２価鉄を含有するフェントン試薬を添加する前記＜１＞に記載の汚染土壌の浄化方法である。
＜３＞ 前記酸化分解工程において、前記汚染土壌に対して、過酸化水素及び２価マンガンを含有するフェントン試薬を添加する前記＜１＞に記載の汚染土壌の浄化方法である。
＜４＞ 前記過酸化水素を、前記汚染土壌に対して、０．０１ｍｏｌ／ｋｇ以上０．０５ｍｏｌ／ｋｇ以下添加する前記＜１＞から＜３＞のいずれかに記載の汚染土壌の浄化方法である。
＜５＞ 前記混合工程において、前記液体を、前記汚染土壌に対して、３０質量％以上添加する前記＜１＞から＜４＞のいずれかに記載の汚染土壌の処理方法である。
＜６＞ 前記酸化分解工程において、前記フェントン試薬を、前記汚染土壌に対して、１０質量％以上添加する前記＜１＞から＜５＞のいずれかに記載の汚染土壌の浄化方法である。
＜７＞ 前記混合工程において、４０℃以上８０℃以下の温度の液体を添加する前記＜１＞から＜６＞のいずれかに記載の汚染土壌の浄化方法である。
＜８＞ 前記混合工程において、６以上１４以下のｐＨの液体を添加する前記＜１＞から＜７＞のいずれかに記載の汚染土壌の浄化方法である。
＜９＞ 前記混合工程及び前記液体除去工程を１回以上行う前記＜１＞から＜８＞のいずれかに記載の汚染土壌の浄化方法である。
＜１０＞ ガソリンにより汚染された汚染土壌に対してｐＨ１２以上のアルカリ性水溶液を添加し、前記汚染土壌と前記アルカリ性水溶液を混合する混合工程と、
前記汚染土壌から前記アルカリ性水溶液を除去する液体除去工程と、
前記液体除去工程の後に、前記汚染土壌に対して過酸化水素及び触媒を含有するフェントン試薬を添加し、前記汚染土壌中の炭化水素化合物を酸化分解する酸化分解工程と、
を含み、前記酸化分解工程を２回以上行い、
前記過酸化水素を、前記汚染土壌に対して０．０１ｍｏｌ／ｋｇ以上０．１ｍｏｌ／ｋｇ以下添加することを特徴とする汚染土壌の浄化方法である。
Means for solving the above problems are as follows. Namely
<1> A mixing step of adding a liquid to contaminated soil contaminated with heavy oil and mixing the contaminated soil and the liquid;
a liquid removing step of removing the liquid from the contaminated soil;
After the liquid removal step, an oxidative decomposition step of adding a Fenton reagent containing hydrogen peroxide and a catalyst to the contaminated soil to oxidatively decompose hydrocarbon compounds in the contaminated soil;
and performing the oxidative decomposition step two or more times,
A method for remediation of contaminated soil, characterized in that the hydrogen peroxide is added to the contaminated soil in an amount of 0.01 mol/kg or more and 0.1 mol/kg or less.
<2> The method for remediation of contaminated soil according to <1>, wherein a Fenton's reagent containing hydrogen peroxide and ferrous iron is added to the contaminated soil in the oxidative decomposition step.
<3> The method for remediation of contaminated soil according to <1>, wherein a Fenton's reagent containing hydrogen peroxide and divalent manganese is added to the contaminated soil in the oxidative decomposition step.
<4> The contaminated soil remediation method according to any one of <1> to <3>, wherein 0.01 mol/kg or more and 0.05 mol/kg or less of hydrogen peroxide is added to the contaminated soil. be.
<5> The method for treating contaminated soil according to any one of <1> to <4>, wherein in the mixing step, 30% by mass or more of the liquid is added to the contaminated soil.
<6> The method for remediation of contaminated soil according to any one of <1> to <5>, wherein 10% by mass or more of the Fenton reagent is added to the contaminated soil in the oxidative decomposition step.
<7> The contaminated soil remediation method according to any one of <1> to <6>, wherein a liquid having a temperature of 40° C. or higher and 80° C. or lower is added in the mixing step.
<8> The method for remediation of contaminated soil according to any one of <1> to <7>, wherein a liquid having a pH of 6 or more and 14 or less is added in the mixing step.
<9> The contaminated soil remediation method according to any one of <1> to <8>, wherein the mixing step and the liquid removing step are performed one or more times.
<10> A mixing step of adding an alkaline aqueous solution having a pH of 12 or higher to contaminated soil contaminated with gasoline and mixing the contaminated soil and the alkaline aqueous solution;
a liquid removing step of removing the alkaline aqueous solution from the contaminated soil;
After the liquid removal step, an oxidative decomposition step of adding a Fenton reagent containing hydrogen peroxide and a catalyst to the contaminated soil to oxidatively decompose hydrocarbon compounds in the contaminated soil;
and performing the oxidative decomposition step two or more times,
A method for remediation of contaminated soil, characterized in that the hydrogen peroxide is added to the contaminated soil in an amount of 0.01 mol/kg or more and 0.1 mol/kg or less.
本発明によると、ガソリン、重油、絶縁油などの低～高炭素数の油類により汚染された汚染土壌を、現場において効率良く浄化することができる汚染土壌の浄化方法を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a contaminated soil remediation method that can efficiently remediate contaminated soil contaminated with low to high carbon number oils such as gasoline, heavy oil, and insulating oil on site.
（汚染土壌の浄化方法）
本発明の汚染土壌の浄化方法は、混合工程と、液体除去工程と、酸化分解工程とを含み、更に必要に応じて、その他の工程を含む。
(Method for Purifying Contaminated Soil)
The method for remediation of contaminated soil of the present invention includes a mixing step, a liquid removal step, an oxidative decomposition step, and, if necessary, other steps.
本発明者らが鋭意検討を重ねた結果、汚染土壌の浄化方法における、フェントン反応などの酸化分解工程の前処理として、液体を添加し、前記汚染土壌と前記液体を混合することで、汚染土壌中の酸化分解されにくい油類、酸化分解阻害物質などを汚染土壌中から前記液体中に移すことができ、前記液体を除去することによって、前記汚染土壌から酸化分解されにくい油類、酸化分解阻害物質などを除くことができるため、酸化分解工程における、汚染土壌の浄化作用を向上させることができることを知見した。
また、上記汚染土壌の浄化方法は、ガソリン、軽油等の低炭素数の油類で汚染された土壌だけではなく、従来のフェントン工法では浄化が難しいＡ重油、Ｂ重油等の高炭素数の油類で汚染された土壌を浄化することができる。
As a result of extensive studies by the present inventors, as a pretreatment for an oxidative decomposition process such as the Fenton reaction in a method for remediation of contaminated soil, a liquid is added, and the contaminated soil and the liquid are mixed to remove the contaminated soil. Oils that are difficult to oxidatively decompose, substances that inhibit oxidative decomposition, etc. can be transferred from the contaminated soil to the liquid, and by removing the liquid, oils that are difficult to be oxidatively decomposed from the contaminated soil, oxidative decomposition inhibitors, etc. can be transferred from the contaminated soil. It has been found that since substances can be removed, the cleaning action of contaminated soil in the oxidative decomposition process can be improved.
In addition, the method for remediation of the above-mentioned contaminated soil can be used not only for soil contaminated with low carbon number oils such as gasoline and light oil, but also for high carbon number oils such as heavy oil A and heavy oil B, which are difficult to clean with the conventional Fenton method. It can purify soil contaminated with
＜混合工程＞
前記混合工程は、炭化水素化合物により汚染された汚染土壌に対して液体を添加し、前記汚染土壌と前記液体を混合する工程である。前記混合工程によって、汚染土壌中の酸化分解されにくい油類、酸化分解阻害物質などを汚染土壌中から液体中に移すことができる。
<Mixing process>
The mixing step is a step of adding a liquid to contaminated soil contaminated with a hydrocarbon compound and mixing the contaminated soil and the liquid. Through the mixing step, oils that are difficult to be oxidatively decomposed and oxidative decomposition inhibitors in the contaminated soil can be transferred from the contaminated soil to the liquid.
前記炭化水素化合物としては、例えば、油類、多環芳香族化合物などが挙げられる。 Examples of the hydrocarbon compounds include oils and polycyclic aromatic compounds.
前記油類としては、例えば、鉱物油類、植物性油類などが挙げられる。これらの油類は、道路工事、トンネル建設工事、再開発工事等の各種建設工事に伴って発生する油類、又は自然由来の油類である。
前記鉱物油類としては、例えば、重油、絶縁油等の中～高炭素数の油、ガソリン等の低炭素数の油、軽油、灯油、ナフサ、機械油、切削油などが挙げられる。
前記重油は、動粘度により、１種（Ａ重油）、２種（Ｂ重油）、３種（Ｃ重油）の３種類に分類され、その規格は、ＪＩＳ Ｋ ２２０５に示される通りである。
前記植物性油類としては、例えば、ヤシ油、パーム油、オリーブ油等の不乾性油、ナタネ油、米ぬか油等の半乾性油、アマニ油等の乾性油などが挙げられる。
Examples of the oils include mineral oils and vegetable oils. These oils are oils generated in various construction works such as road construction, tunnel construction, and redevelopment work, or oils derived from nature.
Examples of the mineral oils include medium to high carbon number oils such as heavy oil and insulating oil, low carbon number oils such as gasoline, light oil, kerosene, naphtha, machine oil, and cutting oil.
The heavy oil is classified into three types, type 1 (heavy oil A), type 2 (heavy oil B), and type 3 (heavy oil C), according to kinematic viscosity.
Examples of the vegetable oils include non-drying oils such as coconut oil, palm oil and olive oil, semi-drying oils such as rapeseed oil and rice bran oil, and drying oils such as linseed oil.
前記多環芳香族化合物としては、例えば、アントラセン、ベンズアントラセン、ベンゾピレンなどが挙げられる。 Examples of the polycyclic aromatic compounds include anthracene, benzanthracene, and benzopyrene.
前記炭化水素化合物により汚染された汚染土壌とは、土壌に対する全石油系炭化水素（Ｔｏｔａｌ Ｐｅｔｒｏｌｅｕｍ Ｈｙｄｒｏｃａｒｂｏｎ：ＴＰＨ）濃度が１０００ｍｇ／ｋｇ以上である土壌、又は油臭や油膜を有する土壌を意味する。
前記ＴＰＨ濃度の試験方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、水素炎イオン化検出器付きガスクロマトグラフ法（ＧＣ－ＦＩＤ法）、赤外分光分析法（ＩＲ法）、重量法（ノルマルヘキサン抽出法）などが挙げられる。これらの中でも、含有する炭素数範囲が明確になり油種を特定しやすい点から、ＧＣ－ＦＩＤ法が好ましい。
前記油臭や油膜の判定方法としては、例えば、「油汚染対策ガイドライン」（平成１８年３月、中央環境審議会）にある土壌及び水の油臭の測定方法、シャーレ法、ビーカー法等による油膜の測定方法などが挙げられる。
The term "contaminated soil contaminated with hydrocarbon compounds" means soil having a total petroleum hydrocarbon (TPH) concentration of 1000 mg/kg or more, or soil having an oily odor or oil film.
The method for testing the TPH concentration is not particularly limited and can be appropriately selected according to the purpose. method), gravimetric method (normal-hexane extraction method), and the like. Among these methods, the GC-FID method is preferable because the range of the number of carbon atoms contained becomes clear and the type of oil can be easily specified.
As the method for determining the oil odor and oil film, for example, the method for measuring the oil odor of soil and water in the "Guidelines for Countermeasures against Oil Pollution" (March 2006, Central Environment Council), the petri dish method, the beaker method, etc. Examples include a method for measuring an oil film.
前記液体としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、水、水溶液などが挙げられる。 The liquid is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include water and aqueous solutions.
前記水としては、例えば、水道水、工業用水、河川水、海水などが挙げられる。
前記水のｐＨとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、６以上１４以下が挙げられる。
Examples of the water include tap water, industrial water, river water, and seawater.
The pH of the water is not particularly limited and can be appropriately selected according to the purpose.
前記水溶液としては、薬剤を前記水で希釈した水溶液などが挙げられる。
前記薬剤としては、例えば、酸性ｐＨ調整剤、アルカリ性ｐＨ調整剤、界面活性剤、有機溶剤などが挙げられる。
前記酸性ｐＨ調整剤としては、例えば、硫酸、塩酸、硝酸、リン酸、酢酸などが挙げられる。これらは、１種単独で使用してもよく、２種以上を併用してもよい。
前記アルカリ性ｐＨ調整剤としては、例えば、苛性ソーダ、炭酸ナトリウム、炭酸水素ナトリウム、リン酸水素二カリウム、リン酸三カリウム、酢酸ナトリウムなどが挙げられる。これらは、１種単独で使用してもよく、２種以上を併用してもよい。
前記界面活性剤としては、例えば、アニオン系界面活性剤、両性界面活性剤、ノニオン系界面活性剤などが挙げられる。これらは、１種単独で使用してもよく、２種以上を併用してもよい。
前記有機溶剤としては、例えば、メタノール、エタノール、１－プロパノール、２－プロパノール、アセトン、テトラヒドロフラン、酢酸エチルなどが挙げられる。これらは、１種単独で使用してもよく、２種以上を併用してもよい。前記有機溶剤の含有量としては、前記水溶液に対して、１質量％以下が好ましい。
前記水溶液としては、酸性水溶液、中性水溶液、アルカリ性水溶液などが挙げられる。これらの中でも、ｐＨが５．８～８．６の中性水溶液、ｐＨが８.６以上のアルカリ性水溶液が好ましい。前記水溶液が、前記中性水溶液、前記アルカリ性水溶液であると、ガソリンに対して、酸化分解工程における高い浄化作用が得られる。また、アルカリ性水溶液で処理をすることによって、濃度低減率の上昇、ｐＨの低下、酸性臭の発生を抑制することができる。
前記酸性水溶液の調製方法としては、水に対して、前記酸性ｐＨ調整剤を添加する方法などが挙げられる。
前記アルカリ性水溶液の調製方法としては、水に対して、前記アルカリ性ｐＨ調整剤を添加する方法などが挙げられる。
Examples of the aqueous solution include an aqueous solution obtained by diluting a drug with water.
Examples of the drug include acidic pH adjusters, alkaline pH adjusters, surfactants, organic solvents, and the like.
Examples of the acidic pH adjuster include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and acetic acid. These may be used individually by 1 type, and may use 2 or more types together.
Examples of the alkaline pH adjuster include caustic soda, sodium carbonate, sodium hydrogen carbonate, dipotassium hydrogen phosphate, tripotassium phosphate, and sodium acetate. These may be used individually by 1 type, and may use 2 or more types together.
Examples of the surfactant include anionic surfactants, amphoteric surfactants, and nonionic surfactants. These may be used individually by 1 type, and may use 2 or more types together.
Examples of the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, acetone, tetrahydrofuran and ethyl acetate. These may be used individually by 1 type, and may use 2 or more types together. As content of the said organic solvent, 1 mass % or less is preferable with respect to the said aqueous solution.
Examples of the aqueous solution include an acidic aqueous solution, a neutral aqueous solution, an alkaline aqueous solution, and the like. Among these, a neutral aqueous solution with a pH of 5.8 to 8.6 and an alkaline aqueous solution with a pH of 8.6 or higher are preferred. When the aqueous solution is the neutral aqueous solution or the alkaline aqueous solution, a high purifying action can be obtained in the oxidative decomposition process for gasoline. In addition, by treating with an alkaline aqueous solution, it is possible to suppress an increase in concentration reduction rate, a decrease in pH, and generation of an acidic odor.
Examples of the method for preparing the acidic aqueous solution include a method of adding the acidic pH adjuster to water.
Examples of the method for preparing the alkaline aqueous solution include a method of adding the alkaline pH adjuster to water.
前記液体の温度としては、特に制限はなく、目的に応じて適宜選択することができるが、酸化分解工程における高い浄化作用が得られる点から、４０℃以上が好ましく、４０℃以上８０℃以下がより好ましく、６０℃以上８０℃以下が特に好ましい。 The temperature of the liquid is not particularly limited and can be appropriately selected according to the purpose, but is preferably 40° C. or higher, and 40° C. or higher and 80° C. or lower, from the viewpoint of obtaining a high purification effect in the oxidative decomposition step. More preferably, 60° C. or higher and 80° C. or lower is particularly preferable.
前記液体の添加量としては、特に制限はなく、目的に応じて適宜選択することができるが、前記汚染土壌に対して、３０質量％以上が好ましい。 The amount of the liquid to be added is not particularly limited and can be appropriately selected according to the purpose, but is preferably 30% by mass or more with respect to the contaminated soil.
前記汚染土壌と前記液体を混合する方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、バックホウ、ポンプ、撹拌機などを用いて混合する方法が挙げられる。前記バックホウは、スケルトンバケット、ミキシングバケットなどを用いると混合精度が向上する。
前記混合の条件は、汚染土壌が前記液体に浸漬されていればよい。
The method for mixing the contaminated soil and the liquid is not particularly limited and can be appropriately selected according to the purpose. The backhoe can improve mixing accuracy by using a skeleton bucket, a mixing bucket, or the like.
The mixing condition may be that the contaminated soil is immersed in the liquid.
前記混合工程の回数は、前記汚染土壌の、ＴＰＨの濃度及び油臭や油膜の低減状況に応じて１回以上が好ましく、２回以上がより好ましい。 The number of times of the mixing step is preferably one or more, more preferably two or more, depending on the concentration of TPH and the state of reduction of oil odor and oil film in the contaminated soil.
＜液体除去工程＞
前記液体除去工程は、前記混合工程後の汚染土壌から、液体を除去する工程である。前記液体除去工程によって、汚染土壌から、酸化分解されにくい油類、酸化分解阻害物質などを前記液体ごと除去することができ、酸化分解工程における、汚染土壌の浄化作用を向上させることができる。
<Liquid removal step>
The liquid removing step is a step of removing liquid from the contaminated soil after the mixing step. By the liquid removal step, it is possible to remove oils that are difficult to be oxidatively decomposed, oxidative decomposition inhibitors, and the like from the contaminated soil together with the liquid, thereby improving the cleaning action of the contaminated soil in the oxidative decomposition step.
前記液体を除去する方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、スクリューデカンタを用いる方法、フィルタープレスを用いる方法、重力沈降を利用して土壌粒子を沈殿させ、上澄みを除去する方法、ポンプを用いる方法などが挙げられる。液体除去工程によって、汚染土壌から、酸化分解されにくい油類、酸化分解阻害物質などを除去することができ、酸化分解工程における処理時間の短縮、浄化処理量を増加させることができる。 The method for removing the liquid is not particularly limited and can be appropriately selected according to the purpose. , the method of removing the supernatant, the method of using a pump, and the like. The liquid removal process can remove oils that are difficult to be oxidatively decomposed, oxidative decomposition inhibitors, and the like from the contaminated soil, thereby shortening the treatment time in the oxidative decomposition process and increasing the amount of purification treatment.
前記汚染土壌から液体を除去した後は、例えば、ＵＶ法、ＩＲ法、ガスクロマトグラフ法などの各種簡易測定法によるＴＰＨの濃度の測定、油臭や油膜の判定を行うことにより、汚染土壌の汚染度合を把握することが好ましい。汚染土壌の汚染度合を把握することで、前記混合工程を繰り返す必要性を判断することができる。 After removing the liquid from the contaminated soil, for example, the concentration of TPH is measured by various simple measurement methods such as the UV method, the IR method, and the gas chromatography method, and the oil odor and oil film are determined. It is preferable to know the degree. By grasping the degree of contamination of the contaminated soil, it is possible to determine the necessity of repeating the mixing step.
前記液体除去工程の回数は、前記汚染土壌の、ＴＰＨの濃度及び油臭や油膜の低減状況に応じて１回以上が好ましく、２回以上がより好ましい。
前記液体除去工程としては、前記混合工程を１回行う毎に、液体除去工程を１回行うことが好ましい。
The number of times of the liquid removal step is preferably one or more, more preferably two or more, depending on the concentration of TPH and the degree of reduction of oil odor and oil film in the contaminated soil.
As the liquid removing step, it is preferable to perform the liquid removing step once every time the mixing step is performed.
＜酸化分解工程＞
前記酸化分解工程は、前記汚染土壌中の炭化水素化合物を酸化分解する工程である。
<Oxidative decomposition process>
The oxidative decomposition step is a step of oxidatively decomposing hydrocarbon compounds in the contaminated soil.
前記炭化水素化合物を酸化分解する方法としては、前記汚染土壌中に、過硫酸、過炭酸、オゾン、ヒドロキシラジカルなどを発生させる方法などが挙げられる。
前記ヒドロキシラジカルを発生させる方法としては、例えば、フェントン反応、紫外線の照射、超音波などが挙げられる。これらの中でも、フェントン反応が好ましい。
前記フェントン反応は、前記汚染土壌に、フェントン試薬を添加することで、ヒドロキシラジカルを発生させる方法であり、前記フェントン試薬としては、酸化剤と触媒を含有することが好ましい。
下記式に示すように、前記酸化剤と前記触媒とのフェントン反応により、ヒドロキシラジカルが発生し、発生したヒドロキシラジカルの酸化力によって、汚染土壌中の炭化水素化合物が酸化分解される。
Ｈ２Ｏ２ ＋ Ｆｅ２＋ → Ｆｅ３＋ ＋ ＯＨ－ ＋ ・ＯＨ
前記フェントン試薬の添加量としては、前記汚染土壌に対して、１０質量％以上が好ましい。前記添加量が、１０質量％以上であると、酸化分解工程における浄化作用が向上する。
Examples of the method of oxidatively decomposing the hydrocarbon compound include a method of generating persulfuric acid, percarbonic acid, ozone, hydroxyl radicals, etc. in the contaminated soil.
Examples of the method for generating the hydroxyl radical include Fenton reaction, irradiation with ultraviolet rays, and ultrasonic waves. Among these, the Fenton reaction is preferred.
The Fenton reaction is a method of generating hydroxyl radicals by adding a Fenton reagent to the contaminated soil, and the Fenton reagent preferably contains an oxidizing agent and a catalyst.
As shown in the following formula, the Fenton reaction between the oxidizing agent and the catalyst generates hydroxyl radicals, and the oxidizing power of the generated hydroxyl radicals oxidatively decomposes hydrocarbon compounds in contaminated soil.
H 2 O 2 + Fe 2+ → Fe 3+ + OH − + OH
The amount of the Fenton reagent to be added is preferably 10% by mass or more with respect to the contaminated soil. When the amount added is 10% by mass or more, the purification action in the oxidative decomposition process is improved.
前記酸化剤としては、例えば、過酸化水素、過酸化カルシウム、過酸化ナトリウム、過マンガン酸塩などの過酸化物が挙げられる。これらの中でも、強力な酸化力を有するヒドロキシラジカルを生成する点から、過酸化水素が好ましい。
前記過酸化水素の添加量は、前記汚染土壌に対して、０．０１ｍｏｌ／ｋｇ以上が好ましい。前記過酸化水素の添加量が、０．０１ｍｏｌ／ｋｇであると、酸化分解工程における浄化作用が向上する。
Examples of the oxidizing agent include peroxides such as hydrogen peroxide, calcium peroxide, sodium peroxide, and permanganate. Among these, hydrogen peroxide is preferred because it produces hydroxyl radicals having strong oxidizing power.
The amount of hydrogen peroxide to be added is preferably 0.01 mol/kg or more with respect to the contaminated soil. When the amount of hydrogen peroxide added is 0.01 mol/kg, the purifying action in the oxidative decomposition process is improved.
前記触媒としては、例えば、２価鉄、３価鉄、２価銅、２価マンガンなどの化合物が挙げられる。これらの中でも、２価鉄、２価マンガンなどの化合物が好ましい。
前記２価鉄の化合物としては、硫酸鉄（ＩＩ）、過塩素酸鉄（ＩＩ）、硝酸鉄（ＩＩ）などが挙げられる。
前記硫酸鉄（ＩＩ）としては、硫酸鉄（ＩＩ）無水和物、硫酸鉄（ＩＩ）一水和物、硫酸鉄（ＩＩ）四水和物、硫酸鉄（ＩＩ）五水和物、硫酸鉄（ＩＩ）七水和物などが挙げられる。これらは、１種単独で使用してもよく、２種以上を併用してもよい。これらの中でも、鉄（ＩＩ）イオンと結合している水分子と過酸化水素が効率よく置き換わる点から、硫酸鉄（ＩＩ）七水和物が好ましい。
前記２価マンガンの化合物としては、硫酸マンガン（ＩＩ）一水和物、硫酸マンガン（ＩＩ）四水和物、硫酸マンガン（ＩＩ）五水和物、硝酸マンガン（ＩＩ）無水和物、硝酸マンガン（ＩＩ）四水和物、硝酸マンガン（ＩＩ）六水和物などが挙げられる。これらの中でも、マンガン（ＩＩ）イオンと結合している水分子と過酸化水素が効率よく置き換わる点から、硫酸マンガン（ＩＩ）五水和物が好ましい。
Examples of the catalyst include compounds such as divalent iron, trivalent iron, divalent copper, and divalent manganese. Among these, compounds such as divalent iron and divalent manganese are preferred.
Examples of the bivalent iron compound include iron (II) sulfate, iron (II) perchlorate, and iron (II) nitrate.
Examples of the iron (II) sulfate include iron (II) sulfate anhydrate, iron (II) sulfate monohydrate, iron (II) sulfate tetrahydrate, iron (II) sulfate pentahydrate, iron sulfate (II) heptahydrate and the like. These may be used individually by 1 type, and may use 2 or more types together. Among these, iron (II) sulfate heptahydrate is preferable because water molecules bound to iron (II) ions are efficiently replaced with hydrogen peroxide.
Examples of the divalent manganese compound include manganese (II) sulfate monohydrate, manganese (II) sulfate tetrahydrate, manganese (II) sulfate pentahydrate, manganese (II) nitrate anhydrate, and manganese nitrate. (II) tetrahydrate, manganese (II) nitrate hexahydrate, and the like. Among these, manganese (II) sulfate pentahydrate is preferred because water molecules bound to manganese (II) ions are efficiently replaced with hydrogen peroxide.
前記触媒の添加量としては、前記汚染土壌に対して、０．０００２ｍｏｌ／ｋｇ以上が好ましく、０．００１ｍｏｌ／ｋｇ以上がより好ましく、０．００２ｍｏｌ／ｋｇ以上が特に好ましい。前記触媒の添加量としては、前記過酸化水素の添加量に対して、モル比として１／５０程度が好ましい。
油類により汚染された前記汚染土壌に、前記液体を添加及び混合した後に、前記液体除去工程を経てから前記フェントン反応を適用することにより、フェントン反応による前記汚染土壌からの油類の除去効果を著しく向上させることができる。
The amount of the catalyst added is preferably 0.0002 mol/kg or more, more preferably 0.001 mol/kg or more, and particularly preferably 0.002 mol/kg or more, relative to the contaminated soil. The amount of the catalyst to be added is preferably about 1/50 as a molar ratio with respect to the amount of hydrogen peroxide to be added.
After adding and mixing the liquid to the contaminated soil contaminated with oils, the Fenton reaction is applied after the liquid removal step, so that the effect of removing oils from the contaminated soil by the Fenton reaction is improved. can be significantly improved.
前記酸化分解工程は、ＴＰＨの濃度及び油臭や油膜の低減状況に応じて１回以上が好ましく、２回以上がより好ましい。 The oxidative decomposition step is preferably performed once or more, more preferably twice or more, depending on the concentration of TPH and the degree of reduction in oil odor and oil film.
＜その他の工程＞
前記その他の工程としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、酸化分解時に発生する上澄みを除去する工程、浄化完了判定工程などが挙げられる。
<Other processes>
The other steps are not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include a step of removing supernatant generated during oxidative decomposition, a step of judging the completion of purification, and the like.
前記酸化分解時に発生する上澄みを除去する工程としては、例えば、スクリューデカンタを用いる方法、フィルタープレスを用いる方法、重力沈降を利用して土壌粒子を沈殿させ、上澄みを除去する方法、ポンプを用いる方法などが挙げられる。
添加したフェントン試薬などが少ない場合、又は酸化分解時に発生した上澄みが少ない場合は、直接、汚染土壌に固化材等の改良材を添加することができる。
Examples of the step of removing the supernatant generated during the oxidative decomposition include a method using a screw decanter, a method using a filter press, a method using gravitational settling to precipitate soil particles and removing the supernatant, and a method using a pump. etc.
When the amount of added Fenton's reagent or the like is small, or when the amount of supernatant generated during oxidative decomposition is small, an improvement material such as a solidification material can be added directly to the contaminated soil.
前記浄化完了判定工程は、汚染土壌の浄化が完了しているかを判定する工程であり、例えば、前記各種簡易測定法などで行うことができる。 The purification completion determination step is a step of determining whether or not the purification of contaminated soil is completed, and can be performed, for example, by the various simple measurement methods described above.
図１は、本発明の汚染土壌の浄化方法のフロー図である。図１を用いて、本発明の汚染土壌の浄化方法の実施形態について説明する。
まず、図１に示す汚染土壌の掘削を、図２に示すようにバックホウなどを用いて行う。
次に、液体をホース又はポンプを用いて、掘削した汚染土壌に添加し、又は添加しながらバックホウを用いてよく混合する。このとき、図３に示すように、汚染土壌と液体を混合容器に投入し、混合容器内で混合することが好ましい。
次に、混合後の汚染土壌から、ポンプなどを用いて液体を除去する。除去された液体は、油分の除去、ｐＨの調整を行った後に排水することが好ましい。
液体が除去された汚染土壌は、ＴＰＨの濃度及び油臭や油膜の低減状況に応じて、液体の添加、混合、除去の処理を繰り返し行うことが好ましい。
次に、液体が除去された汚染土壌に、酸化剤及び触媒を含有するフェントン試薬をホース又はポンプを用いて添加し、バックホウを用いてよく混合する。このとき、図３に示すように、汚染土壌とフェントン試薬を混合容器に投入し、混合容器内で混合することが好ましい。これにより、汚染土壌の量を把握することができ、適量のフェントン試薬を汚染土壌に添加することができる。また、フェントン試薬は、酸化剤と触媒を混合すると瞬時にヒドロキシラジカルが発生するため、酸化剤と触媒の混合は、汚染土壌に投入する直前に行うことが好ましい。フェントン試薬を添加後は、酸化分解反応が停止するまで放置する。
次に、酸化分解反応停止後の土壌から、ポンプなどを用いて上澄みを除去する。除去された上澄みは、ｐＨの調整を行った後、また、必要に応じて油分の除去を行った後に排水することが好ましい。
フェントン試薬が除去された浄化後の土壌は、ＴＰＨの濃度及び油臭や油膜の低減状況に応じて、フェントン試薬の添加、混合、反応停止後の上澄みの除去の処理を繰り返し行うことが好ましい。
次に、浄化後の土壌の含水調整を行い、浄化後の土壌を埋戻す。前記含水調整の方法としては、例えば、天日干し、固化材等の改良材の添加、フィルタープレスなどの方法が挙げられる。
FIG. 1 is a flow chart of the contaminated soil purification method of the present invention. An embodiment of the contaminated soil purification method of the present invention will be described with reference to FIG.
First, the contaminated soil shown in FIG. 1 is excavated using a backhoe or the like as shown in FIG.
The liquid is then added to the excavated contaminated soil using a hose or pump or mixed well using a backhoe while adding. At this time, as shown in FIG. 3, it is preferable to put the contaminated soil and the liquid into a mixing container and mix them in the mixing container.
Next, liquid is removed from the mixed contaminated soil using a pump or the like. The removed liquid is preferably drained after removal of oil and adjustment of pH.
The contaminated soil from which the liquid has been removed is preferably subjected to repeated liquid addition, mixing, and removal treatments depending on the concentration of TPH and the state of reduction of oil odor and oil film.
Fenton's reagent containing oxidant and catalyst is then added to the contaminated soil from which the liquid has been removed using a hose or pump and mixed well using a backhoe. At this time, as shown in FIG. 3, it is preferable to put the contaminated soil and Fenton's reagent into a mixing container and mix them in the mixing container. Thereby, the amount of contaminated soil can be grasped, and an appropriate amount of Fenton's reagent can be added to the contaminated soil. In addition, since the Fenton's reagent instantly generates hydroxyl radicals when the oxidizing agent and the catalyst are mixed, the oxidizing agent and the catalyst are preferably mixed immediately before being introduced into the contaminated soil. After adding Fenton's reagent, it is left until the oxidative decomposition reaction stops.
Next, a pump or the like is used to remove the supernatant from the soil after the oxidative decomposition reaction has stopped. The removed supernatant is preferably drained after adjusting the pH and, if necessary, removing oil.
The purified soil from which the Fenton reagent has been removed is preferably repeatedly subjected to the addition of the Fenton reagent, mixing, and removal of the supernatant after stopping the reaction, depending on the concentration of TPH and the reduction in oil odor and oil film.
Next, the water content of the purified soil is adjusted, and the purified soil is backfilled. Examples of the method for adjusting the water content include drying in the sun, addition of improving agents such as solidifying agents, and filter press.
以下、本発明の実施例を説明するが、本発明は、これらの実施例に何ら限定されるものではない。なお、以下の実施例では、設備の関係からラボスケールで実験を行ったが、現場において実施しても同様の効果が得られるものである。 Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples, the experiments were conducted on a laboratory scale due to equipment limitations.
（実施例１）
－Ａ重油汚染土壌の調製－
重油で汚染されている汚染土壌を採取した。Ａ重油を貯蔵していたタンクおよび配管付近の漏洩箇所から採取した汚染土壌をＡ重油汚染土壌とし、ＧＣ－ＦＩＤ法によって炭素数範囲を確認した。前記Ａ重油汚染土壌のＴＰＨ濃度を、前記簡易測定法のＵＶ法によって測定したところ、３，９００ｍｇ／ｋｇであった。同一敷地内の同一の土質である非汚染土壌を採取し、前記非汚染土壌と前記Ａ重油汚染土壌とを混合することで、試験土壌（前記Ａ重油汚染土壌）におけるＴＰＨの濃度を調整した。前記ＴＰＨの濃度測定を、混合工程後、及び酸化分解工程後に実施した。
(Example 1)
-Preparation of A heavy oil contaminated soil-
Contaminated soil contaminated with heavy oil was sampled. Contaminated soil sampled from a tank storing A heavy oil and a leak point near a pipe was used as A heavy oil contaminated soil, and the carbon number range was confirmed by the GC-FID method. When the TPH concentration of the A heavy oil contaminated soil was measured by the UV method of the simple measurement method, it was 3,900 mg/kg. Uncontaminated soil of the same soil quality was collected from the same site, and the uncontaminated soil and the A heavy oil contaminated soil were mixed to adjust the concentration of TPH in the test soil (the A heavy oil contaminated soil). The TPH concentration measurements were performed after the mixing step and after the oxidative decomposition step.
－混合工程－
容器に前記Ａ重油汚染土壌３００ｇ、液体として水９０ｇを添加し、５分間混合した。
上記工程を１回行った。
-Mixing process-
300 g of the A heavy oil contaminated soil and 90 g of water as a liquid were added to the container and mixed for 5 minutes.
The above steps were performed once.
－液体除去工程－
前記混合工程後、容器中の上澄みを除去した。
上記工程を１回行った。
-Liquid removal process-
After the mixing step, the supernatant in the container was removed.
The above steps were performed once.
－酸化分解工程－
混合工程後のＡ重油汚染土壌３００ｇに下記組成のフェントン試薬３０ｇを添加し、５分間混合した。その後、混合後のＡ重油汚染土壌を、室温で一晩放置した。その後、Ａ重油汚染土壌から、上澄みを除いた後に風乾した。
上記酸化分解工程を３回行った。
［フェントン試薬］
・過酸化水素（富士フイルム和光純薬株式会社製） ０．３４質量％
・硫酸鉄（II）七水和物（富士フイルム和光純薬株式会社製） ０．００１質量％
・水 ９９．６６質量％
［ＵＶ法］
・土壌油分抽出試薬（株式会社共立理化学研究所製）
-Oxidative decomposition process-
30 g of Fenton's reagent having the following composition was added to 300 g of A heavy oil-contaminated soil after the mixing step, and mixed for 5 minutes. After that, the A heavy oil contaminated soil after mixing was left overnight at room temperature. Thereafter, the A heavy oil contaminated soil was air-dried after removing the supernatant.
The oxidative decomposition step was performed three times.
[Fenton reagent]
・ Hydrogen peroxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) 0.34% by mass
・ Iron sulfate (II) heptahydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) 0.001% by mass
・Water 99.66% by mass
[UV method]
・Soil oil extraction reagent (manufactured by Kyoritsu Chemical Laboratory Co., Ltd.)
（実施例２～１７及び比較例１～９）
実施例１において、フェントン試薬の組成、液体、混合工程の回数、液体除去工程の回数、酸化分解工程の回数を表１～表３に示すように変更した以外は、実施例１と同様にして、実施例２～１７及び比較例１～９の汚染土壌の浄化方法を行った。
(Examples 2 to 17 and Comparative Examples 1 to 9)
In Example 1, the same procedure as in Example 1 was performed except that the composition of the Fenton reagent, the liquid, the number of mixing steps, the number of liquid removal steps, and the number of oxidative decomposition steps were changed as shown in Tables 1 to 3. , Examples 2 to 17 and Comparative Examples 1 to 9 were used for remediation of contaminated soil.
実施例１～１７及び比較例１～９の汚染土壌の浄化方法による、浄化後の土壌のＴＰＨ濃度の測定を行い、浄化方法の評価を行った。結果を表４に示す。 The TPH concentration of the soil after purification was measured by the contaminated soil purification method of Examples 1 to 17 and Comparative Examples 1 to 9, and the purification method was evaluated. Table 4 shows the results.
実施例１～１７の評価結果より、混合工程及び酸化分解工程を１回以上行うことで、従来のフェントン工法では、浄化が難しいＡ重油汚染土壌を浄化できることが確認された。また、実施例９の結果より、混合工程における液体の温度を６０℃とすることで、Ａ重油汚染土壌の高い浄化作用が確認された。 From the evaluation results of Examples 1 to 17, it was confirmed that by performing the mixing step and the oxidative decomposition step one or more times, it was possible to purify A-heavy oil-contaminated soil, which is difficult to purify by the conventional Fenton method. Further, from the results of Example 9, it was confirmed that by setting the temperature of the liquid in the mixing step to 60° C., a high remediation action for A-heavy oil-contaminated soil was obtained.
（実施例１８）
－Ｂ重油汚染土壌の調製－
重油で汚染されている汚染土壌を採取した。Ｂ重油を貯蔵していたタンクおよび配管付近の漏洩箇所から採取した汚染土壌をＢ重油汚染土壌とし、ＧＣ－ＦＩＤ法によって炭素数範囲を確認した。前記Ｂ重油汚染土壌のＴＰＨ濃度を、前記簡易測定法のＵＶ法によって、測定したところ５，１００ｍｇ／ｋｇであった。同一敷地内の同一の土質である非汚染土壌を採取し、前記非汚染土壌と前記Ｂ重油汚染土壌とを混合することで、試験土壌（前記Ｂ重油汚染土壌）におけるＴＰＨの濃度を調整した。前記ＴＰＨの濃度測定を、混合工程後、及び酸化分解工程後に実施した。
(Example 18)
-Preparation of B heavy oil contaminated soil-
Contaminated soil contaminated with heavy oil was sampled. Contaminated soil sampled from the tank storing B heavy oil and the leakage point near the piping was used as B heavy oil contaminated soil, and the carbon number range was confirmed by the GC-FID method. The TPH concentration of the B heavy oil contaminated soil was measured by the UV method, which is the simple measurement method, and found to be 5,100 mg/kg. Uncontaminated soil of the same soil quality was collected from the same site, and the uncontaminated soil and the B heavy oil contaminated soil were mixed to adjust the concentration of TPH in the test soil (the B heavy oil contaminated soil). The TPH concentration measurements were performed after the mixing step and after the oxidative decomposition step.
－混合工程－
容器に前記Ｂ重油汚染土壌３００ｇ、液体として水９０ｇを添加し、５分間混合した。
上記混合工程を１回行った。
-Mixing process-
300 g of the B heavy oil contaminated soil and 90 g of water as a liquid were added to the container and mixed for 5 minutes.
The above mixing step was performed once.
－液体除去工程－
前記混合工程後、容器中の上澄みを除去した。
上記液体除去工程を１回行った。
-Liquid removal process-
After the mixing step, the supernatant in the container was removed.
The above liquid removal step was performed once.
－酸化分解工程－
混合工程後のＢ重油汚染土壌３００ｇに下記組成のフェントン試薬３０ｇを添加し、５分間混合した。その後、混合後のＢ重油汚染土壌を、室温で一晩放置した。その後、Ｂ重油汚染土壌から上澄みを除いた後に風乾した。
上記酸化分解工程を３回行った。
［フェントン試薬］
・過酸化水素（富士フイルム和光純薬株式会社製） ０．３４質量％
・硫酸鉄（II）七水和物（富士フイルム和光純薬株式会社製） ０．００１質量％
・水 ９９．６６質量％
［ＵＶ法］
・土壌油分抽出試薬（株式会社共立理化学研究所製）
-Oxidative decomposition process-
30 g of Fenton's reagent having the following composition was added to 300 g of B heavy oil-contaminated soil after the mixing step, and mixed for 5 minutes. After that, the B heavy oil-contaminated soil after mixing was left overnight at room temperature. After removing the supernatant from the B heavy oil contaminated soil, the soil was air-dried.
The oxidative decomposition step was performed three times.
[Fenton reagent]
・ Hydrogen peroxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) 0.34% by mass
・ Iron sulfate (II) heptahydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) 0.001% by mass
・Water 99.66% by mass
[UV method]
・Soil oil extraction reagent (manufactured by Kyoritsu Chemical Laboratory Co., Ltd.)
（実施例１９～２３及び比較例１０～１４）
実施例１８において、フェントン試薬の組成、液体、混合工程の回数、液体除去工程の回数、酸化分解工程の回数を表５及び表６に示すように変更した以外は、実施例１８と同様にして、実施例１９～２３及び比較例１０～１４の汚染土壌の浄化方法を行った。
(Examples 19-23 and Comparative Examples 10-14)
In Example 18, the same procedure as in Example 18 was performed except that the composition of the Fenton reagent, the liquid, the number of mixing steps, the number of liquid removal steps, and the number of oxidative decomposition steps were changed as shown in Tables 5 and 6. , Examples 19 to 23 and Comparative Examples 10 to 14 were used for remediation of contaminated soil.
実施例１８～２３及び比較例１０～１４の汚染土壌の浄化方法による、浄化後の土壌のＴＰＨ濃度を、実施例１～１７及び比較例１～９と同様の方法で測定を行い、浄化方法の評価を行った。結果を表７に示す。 The TPH concentration of the soil after purification by the contaminated soil purification method of Examples 18 to 23 and Comparative Examples 10 to 14 was measured in the same manner as in Examples 1 to 17 and Comparative Examples 1 to 9, and the purification method was evaluated. Table 7 shows the results.
実施例１８～２３の評価結果より、混合工程及び酸化分解工程を１回以上行うことで、従来のフェントン工法では、浄化が難しいＢ重油汚染土壌を浄化できることが確認された。 From the evaluation results of Examples 18 to 23, it was confirmed that B heavy oil-contaminated soil, which is difficult to clean up by the conventional Fenton method, can be cleaned up by performing the mixing step and the oxidative decomposition step one or more times.
（参考例２４）
－ガソリン汚染土壌の調製－
汚染されていない土壌に、市販のガソリンを添加後、よく混合し、ガソリン汚染土壌を調製した。前記ガソリン汚染土壌のＴＰＨ濃度を、前記簡易分記法のＩＲ法によって、測定したところ２，５００ｍｇ／ｋｇであった。前記ＴＰＨの濃度測定を、混合工程後、及び酸化分解工程後に実施した。
( Reference example 24)
－Preparation of gasoline-contaminated soil－
After adding commercially available gasoline to uncontaminated soil, the mixture was thoroughly mixed to prepare gasoline-contaminated soil. The TPH concentration of the gasoline-contaminated soil was 2,500 mg/kg when measured by the IR method of the simplified fractionation method. The TPH concentration measurements were performed after the mixing step and after the oxidative decomposition step.
－混合工程－
前記ガソリン汚染土壌３００ｇに、水９０ｇを添加し５分間混合した。
上記混合工程を１回行った。
-Mixing process-
90 g of water was added to 300 g of the gasoline-contaminated soil and mixed for 5 minutes.
The above mixing step was performed once.
－液体除去工程－
前記混合工程後、容器中の上澄みを除去した。
上記液体除去工程を１回行った。
-Liquid removal process-
After the mixing step, the supernatant in the container was removed.
The above liquid removal step was performed once.
－酸化分解工程－
混合工程後のガソリン汚染土壌３００ｇに下記組成のフェントン試薬３０ｇを添加し、５分間混合した。その後、混合後のガソリン汚染土壌を室温で一晩放置した。その後、ガソリン汚染土壌から、上澄みを除いた。
上記酸化分解工程を３回行った。
［フェントン試薬］
・過酸化水素（富士フイルム和光純薬株式会社製） ３．４質量％
・硫酸鉄（II）七水和物（富士フイルム和光純薬株式会社製） ０．０１質量％
・水 ９６．５９質量％
［ＩＲ法］
・油分抽出専用溶媒（株式会社堀場アドバンスドテクノ製）
-Oxidative decomposition process-
30 g of Fenton's reagent having the following composition was added to 300 g of the gasoline-contaminated soil after the mixing step and mixed for 5 minutes. After that, the mixed gasoline-contaminated soil was left overnight at room temperature. After that, the supernatant was removed from the gasoline-contaminated soil.
The oxidative decomposition step was performed three times.
[Fenton reagent]
・ Hydrogen peroxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) 3.4% by mass
・ Iron sulfate (II) heptahydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) 0.01% by mass
・Water 96.59% by mass
[IR method]
・Exclusive solvent for oil extraction (manufactured by Horiba Advanced Techno Co., Ltd.)
（実施例２５）
参考例２４において、フェントン試薬の組成、液体、混合工程の回数、液体除去工程の回数、酸化分解工程の回数を表８に示すように変更した以外は、参考例２４と同様にして、実施例２５及び比較例１５～１７の汚染土壌の浄化方法を行った。
(Example 25)
In Reference Example 24, Example 25 and Comparative Examples 15 to 17 for remediation of contaminated soil.
参考例２４、実施例２５及び比較例１５～１７の汚染土壌の浄化方法による、浄化後の土壌のＴＰＨ濃度を、実施例１～１７及び比較例１～９と同様の方法で測定を行い、浄化方法の評価を行った。結果を表９に示す。 Reference Example 24 , Example 25 and Comparative Examples 15 to 17 The TPH concentration of the soil after purification by the contaminated soil purification method was measured in the same manner as in Examples 1 to 17 and Comparative Examples 1 to 9, The purification method was evaluated. Table 9 shows the results.
実施例２４～２５の評価結果より、混合工程及び酸化分解工程を１回以上行うことで、従来のフェントン工法よりもガソリン汚染土壌を浄化できることが確認された。また、実施例２５の結果より、混合工程における液体のｐＨを１２以上（アルカリ性水溶液）とすることで、ガソリン汚染土壌の高い浄化作用が確認された。
From the evaluation results of Examples 24 and 25, it was confirmed that the gasoline-contaminated soil could be purified more than the conventional Fenton method by performing the mixing step and the oxidative decomposition step one or more times. Further, from the results of Example 25, it was confirmed that the pH of the liquid in the mixing step was set to 12 or higher (alkaline aqueous solution), and a high remediation action for gasoline-contaminated soil was confirmed.
Claims (10)
前記汚染土壌から前記液体を除去する液体除去工程と、
前記液体除去工程の後に、前記汚染土壌に対して過酸化水素及び触媒を含有するフェントン試薬を添加し、前記汚染土壌中の炭化水素化合物を酸化分解する酸化分解工程と、
を含み、前記酸化分解工程を２回以上行い、
前記過酸化水素を、前記汚染土壌に対して０．０１ｍｏｌ／ｋｇ以上０．１ｍｏｌ／ｋｇ以下添加することを特徴とする汚染土壌の浄化方法。 a mixing step of adding a liquid to contaminated soil contaminated with heavy oil and mixing the contaminated soil and the liquid;
a liquid removing step of removing the liquid from the contaminated soil;
After the liquid removal step, an oxidative decomposition step of adding a Fenton reagent containing hydrogen peroxide and a catalyst to the contaminated soil to oxidatively decompose hydrocarbon compounds in the contaminated soil;
and performing the oxidative decomposition step two or more times,
A method for remediation of contaminated soil, characterized in that the hydrogen peroxide is added to the contaminated soil in an amount of 0.01 mol/kg or more and 0.1 mol/kg or less.
前記汚染土壌から前記アルカリ性水溶液を除去する液体除去工程と、a liquid removing step of removing the alkaline aqueous solution from the contaminated soil;
前記液体除去工程の後に、前記汚染土壌に対して過酸化水素及び触媒を含有するフェントン試薬を添加し、前記汚染土壌中の炭化水素化合物を酸化分解する酸化分解工程と、After the liquid removal step, an oxidative decomposition step of adding a Fenton reagent containing hydrogen peroxide and a catalyst to the contaminated soil to oxidatively decompose hydrocarbon compounds in the contaminated soil;
を含み、前記酸化分解工程を２回以上行い、and performing the oxidative decomposition step two or more times,
前記過酸化水素を、前記汚染土壌に対して０．０１ｍｏｌ／ｋｇ以上０．１ｍｏｌ／ｋｇ以下添加することを特徴とする汚染土壌の浄化方法。A method for remediation of contaminated soil, characterized in that the hydrogen peroxide is added to the contaminated soil in an amount of 0.01 mol/kg or more and 0.1 mol/kg or less.
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