JP7478605B2 - Soil washing agent composition, multi-type soil washing agent, and method for washing excavated soil - Google Patents
Soil washing agent composition, multi-type soil washing agent, and method for washing excavated soil Download PDFInfo
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- 239000002689 soil Substances 0.000 title claims description 174
- 239000000203 mixture Substances 0.000 title claims description 79
- 238000005406 washing Methods 0.000 title claims description 69
- 239000003795 chemical substances by application Substances 0.000 title claims description 59
- 238000000034 method Methods 0.000 title claims description 40
- -1 polyoxyethylene Polymers 0.000 claims description 58
- 238000004140 cleaning Methods 0.000 claims description 54
- 125000000217 alkyl group Chemical group 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 41
- 239000003208 petroleum Substances 0.000 claims description 37
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 125000003342 alkenyl group Chemical group 0.000 claims description 26
- 239000003945 anionic surfactant Substances 0.000 claims description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000693 micelle Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 239000003921 oil Substances 0.000 description 11
- 159000000000 sodium salts Chemical class 0.000 description 10
- 239000012459 cleaning agent Substances 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 239000004927 clay Substances 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
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- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
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- 239000002027 dichloromethane extract Substances 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005639 Lauric acid Chemical class 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical class CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
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- 239000003349 gelling agent Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
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- 239000010721 machine oil Substances 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
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- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
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- Detergent Compositions (AREA)
Description
本発明は、土壌用洗浄剤組成物、多剤型土壌用洗浄剤及び掘削土壌の洗浄方法に関する。 The present invention relates to a soil cleaning agent composition, a multi-agent soil cleaning agent, and a method for cleaning excavated soil.
石油コンビナート、ガソリンスタンド、貯蔵タンク、化学工場など、油を扱う施設や設備の敷地や跡地では、長期にわたる使用などに伴う油の漏出により、土壌が油で汚染されることがある。このような汚染土壌の浄化方法としては、例えば、土壌を洗浄する、土壌を加熱する、土壌を吸着剤で処理する、化学的に分解する、微生物により分解する（バイオレメディエーション）などの方法が知られている。これらの中で、土壌を洗浄する方法は、汚れの対象が広い、バイオレメディエーション等の前処理工程としても利用できる、汚染土壌の処理量が大きい、などの利点があるとされている。 At the sites or former sites of facilities and equipment that handle oil, such as petroleum refineries, gas stations, storage tanks, and chemical plants, soil can become contaminated with oil due to oil leaks caused by long-term use. Known methods for purifying such contaminated soil include washing the soil, heating the soil, treating the soil with adsorbents, chemically decomposing the soil, and decomposing the soil with microorganisms (bioremediation). Of these, soil washing methods are considered to have the advantages of being applicable to a wide range of contaminants, being usable as a pretreatment process for bioremediation, and being able to treat a large amount of contaminated soil.
特許文献１には、ノニオン系界面活性剤、アニオン系界面活性剤、両性界面活性剤より選ばれた１種又は２種以上を土壌に添加し、土壌を洗浄する土壌の洗浄方法が開示されている。 Patent Document 1 discloses a method for washing soil in which one or more surfactants selected from nonionic surfactants, anionic surfactants, and amphoteric surfactants are added to the soil and the soil is washed.
油などの汚染物質は、シルト、粘土のような細粒土に吸着されやすく、しかも一旦吸着した汚れは洗浄では落としにくいものとなる。また、土壌を洗浄する際の条件、例えば温度、時間、工程数などは、作業現場において様々であるため、条件によらず安定した洗浄力を発現することが望まれる。 Oil and other contaminants are easily adsorbed by fine-grained soil such as silt and clay, and once adsorbed, the dirt is difficult to remove by washing. In addition, conditions for washing soil, such as temperature, time, and number of steps, vary from work site to work, so it is desirable for the cleaning agent to have a stable cleaning power regardless of the conditions.
本発明は、石油系化合物により汚染された土壌、例えばそのような汚れを含む掘削土壌に対する洗浄力に優れ、且つその洗浄力が様々な処理条件で安定して発現する土壌用洗浄剤組成物、多剤型土壌用洗浄剤及び掘削土壌の洗浄方法を提供する。 The present invention provides a soil cleaner composition, a multi-agent soil cleaner, and a method for cleaning excavated soil that have excellent cleaning power for soil contaminated with petroleum compounds, such as excavated soil containing such contaminants, and that exhibit this cleaning power stably under various treatment conditions.
本発明は、（Ａ）アルキル基又はアルケニル基の炭素数が１０以上１８以下であり、エチレンオキシドの平均付加モル数が３以上１０以下のポリオキシエチレンアルキル又はアルケニルエーテル〔以下、（Ａ）成分という〕と、（Ｂ）分子量２００以上１０００以下の陰イオン界面活性剤〔以下、（Ｂ）成分という〕と、水とを含有し、（Ａ）成分の含有量と（Ｂ）成分の含有量の合計に対する（Ｂ）成分の含有量の比率である（Ｂ）／〔（Ａ）＋（Ｂ）〕が３質量％以上２５質量％以下である、石油系化合物により汚染された土壌を洗浄する、土壌用洗浄剤組成物に関する。 The present invention relates to a soil washing agent composition for washing soil contaminated with petroleum compounds, which contains (A) a polyoxyethylene alkyl or alkenyl ether having an alkyl or alkenyl group with 10 to 18 carbon atoms and an average number of moles of ethylene oxide added of 3 to 10 [hereinafter referred to as component (A)], (B) an anionic surfactant having a molecular weight of 200 to 1000 [hereinafter referred to as component (B)], and water, and in which the ratio of the content of component (B) to the total content of component (A) and component (B) (B)/[(A)+(B)]) is 3% by mass to 25% by mass.
また、本発明は、（Ａ）アルキル基又はアルケニル基の炭素数が１０以上１８以下であり、エチレンオキシドの平均付加モル数が３以上１０以下のポリオキシエチレンアルキル又はアルケニルエーテル〔以下、（Ａ）成分という〕を含有する剤（Ａ）と、（Ｂ）分子量２００以上１０００以下の陰イオン界面活性剤〔以下、（Ｂ）成分という〕を含有する剤（Ｂ）とを含む多剤型土壌用洗浄剤であって、
剤（Ａ）及び剤（Ｂ）の少なくとも一方が水を含有し、
剤（Ａ）と剤（Ｂ）とを混合して、（Ａ）成分の含有量と（Ｂ）成分の含有量の合計に対する（Ｂ）成分の含有量の比率である（Ｂ）／〔（Ａ）＋（Ｂ）〕が３質量％以上２５質量％以下である、石油系化合物により汚染された土壌を洗浄する土壌用洗浄剤組成物を調製するために用いられる、
多剤型土壌用洗浄剤に関する。
The present invention also relates to a multi-agent soil washing agent comprising: (A) an agent (A) containing a polyoxyethylene alkyl or alkenyl ether having an alkyl or alkenyl group with 10 or more and 18 or less carbon atoms and an average number of moles of ethylene oxide added of 3 or more and 10 or less [hereinafter referred to as component (A)]; and (B) an agent (B) containing an anionic surfactant having a molecular weight of 200 or more and 1,000 or less [hereinafter referred to as component (B)],
At least one of the agent (A) and the agent (B) contains water;
The agent (A) and the agent (B) are mixed to prepare a soil washing agent composition for washing soil contaminated by petroleum-based compounds, in which the ratio of the content of the (B) component to the total content of the (A) component and the (B) component, that is, (B)/[(A)+(B)], is 3 mass% or more and 25 mass% or less.
This relates to a multi-agent soil cleaner.
また、本発明は、石油系化合物により汚染された掘削土壌を、（Ａ）アルキル基又はアルケニル基の炭素数が１０以上１８以下であり、エチレンオキシドの平均付加モル数が３以上１０以下のポリオキシエチレンアルキル又はアルケニルエーテル〔以下、（Ａ）成分という〕と、（Ｂ）分子量２００以上１０００以下の陰イオン界面活性剤〔以下、（Ｂ）成分という〕と、水とを用いて洗浄する、掘削土壌の洗浄方法であって、
（Ａ）成分と（Ｂ）成分とを、（Ａ）成分と（Ｂ）成分との合計に対する（Ｂ）成分の比率である（Ｂ）／〔（Ａ）＋（Ｂ）〕が３質量％以上２５質量％以下となるように用いる、
掘削土壌の洗浄方法に関する。
The present invention also relates to a method for washing excavated soil contaminated with petroleum compounds, comprising washing the excavated soil with (A) a polyoxyethylene alkyl or alkenyl ether having an alkyl or alkenyl group with 10 to 18 carbon atoms and an average number of moles of ethylene oxide added of 3 to 10 (hereinafter referred to as component (A)), (B) an anionic surfactant having a molecular weight of 200 to 1,000 (hereinafter referred to as component (B)), and water,
The component (A) and the component (B) are used in such a manner that the ratio of the component (B) to the total of the components (A) and (B), that is, (B)/[(A)+(B)], is 3 mass% or more and 25 mass% or less.
This invention relates to a method for washing excavated soil.
本発明によれば、石油系化合物により汚染された掘削土壌に対する洗浄力に優れ、且つその洗浄力が様々な処理条件で安定して発現する土壌用洗浄剤組成物、多剤型土壌用洗浄剤及び掘削土壌の洗浄方法が提供される。本発明は、細粒分が多い掘削土壌に対しても優れた油汚れ洗浄力を示す。以下、土壌という場合は、石油系化合物により汚染された掘削土壌を含む。 According to the present invention, there are provided a soil cleaner composition, a multi-agent soil cleaner, and a method for cleaning excavated soil, which have excellent cleaning power for excavated soil contaminated with petroleum-based compounds and which exhibit this cleaning power stably under various treatment conditions. The present invention also exhibits excellent oil stain cleaning power for excavated soil containing a large amount of fine particles. Hereinafter, the term "soil" includes excavated soil contaminated with petroleum-based compounds.
＜土壌用洗浄剤組成物＞
本発明の土壌用洗浄剤組成物は、石油系化合物により汚染された土壌に対して優れた油汚れ洗浄力を示す。その理由は必ずしも明らかではないが、本発明では、（Ｂ）成分を所定の比率で（Ａ）成分と併用することで、混合ミセルなどの様々なミセルが形成され、それらには石油系化合物に浸透しやすいもの、石油系化合物を乳化しやすいものが混在し、（Ａ）成分と（Ｂ）成分の石油系化合物への浸透が促進され、石油系化合物が乳化しやすい状態に改質され、その結果、石油系化合物が土壌から分離しやすくなるためではないかと推察される。
<Soil Cleaning Agent Composition>
The soil cleaner composition of the present invention shows excellent oil stain cleaning power for soil contaminated with petroleum-based compounds. The reason for this is not necessarily clear, but it is presumed that this is because in the present invention, by using component (B) in combination with component (A) at a predetermined ratio, various micelles such as mixed micelles are formed, among which some are easily permeated into petroleum-based compounds and some are easily emulsified into petroleum-based compounds, which promotes the permeation of components (A) and (B) into petroleum-based compounds, modifying the petroleum-based compounds to a state that is easily emulsified, and as a result, the petroleum-based compounds are easily separated from the soil.
〔（Ａ）成分〕
（Ａ）成分は、アルキル基又はアルケニル基の炭素数が１０以上１８以下であり、エチレンオキシドの平均付加モル数が３以上１０以下のポリオキシエチレンアルキル又はアルケニルエーテルである。
（Ａ）成分のアルキル基又はアルケニル基は、直鎖でも分岐鎖でもよいが、（Ｂ）成分との混合ミセル形成の観点から、直鎖が好ましい。
（Ａ）成分のアルキル基又はアルケニル基の炭素数は、好ましくは１６以下、より好ましくは１４以下である。（Ａ）成分のアルキル基又はアルケニル基の炭素数は、モル濃度の観点から、１０又は１２が好ましい。
（Ａ）成分のエチレンオキシドの平均付加モル数は、浸透された石油系化合物の乳化の観点から、好ましくは３以上、そして、石油系化合物への浸透の観点から、好ましくは８以下である。
（Ａ）成分は、アルキル基を有するもの、すなわち、水溶性の観点から、ポリオキシエチレンアルキルエーテルが好ましい。
[Component (A)]
Component (A) is a polyoxyethylene alkyl or alkenyl ether having an alkyl or alkenyl group with 10 or more and 18 or less carbon atoms and an average added mole number of ethylene oxide of 3 or more and 10 or less.
The alkyl or alkenyl group of the component (A) may be either straight-chain or branched-chain; from the viewpoint of forming mixed micelles with the component (B), the straight-chain group is preferred.
The number of carbon atoms in the alkyl or alkenyl group of component (A) is preferably 16 or less, and more preferably 14 or less. The number of carbon atoms in the alkyl or alkenyl group of component (A) is preferably 10 or 12 from the viewpoint of molar concentration.
The average number of moles of ethylene oxide added in the component (A) is preferably 3 or more from the viewpoint of emulsifying the permeated petroleum-based compound, and is preferably 8 or less from the viewpoint of permeation into the petroleum-based compound.
The component (A) is preferably one having an alkyl group, that is, a polyoxyethylene alkyl ether from the viewpoint of water solubility.
（Ａ）成分は、石油系化合物への浸透、及び浸透された石油系化合物の乳化の観点から、グリフィン法によるＨＬＢが、８．０以上、更に９．０以上、そして、１４．０以下、更に１２．０以下であることが好ましい。 From the viewpoint of penetration into petroleum-based compounds and emulsification of the penetrated petroleum-based compounds, it is preferable that the HLB of component (A) according to the Griffin method is 8.0 or more, more preferably 9.0 or more, and 14.0 or less, more preferably 12.0 or less.
〔（Ｂ）成分〕
（Ｂ）成分は、分子量２００以上１０００以下の陰イオン界面活性剤である。
（Ｂ）成分の分子量は、（Ａ）成分との混合ミセル形成の観点から、２００以上、好ましくは２５０以上、そして、１０００以下、より好ましくは６００以下である。
[Component (B)]
The component (B) is an anionic surfactant having a molecular weight of 200 or more and 1,000 or less.
The molecular weight of component (B) is 200 or more, preferably 250 or more, and 1000 or less, more preferably 600 or less, from the viewpoint of forming mixed micelles with component (A).
（Ｂ）成分としては、脂肪酸塩、硫酸エステル塩、スルホン酸塩、及び燐酸エステル塩から選ばれる、分子量２００以上１０００以下の陰イオン界面活性剤が挙げられる。 Component (B) includes an anionic surfactant selected from fatty acid salts, sulfate ester salts, sulfonate salts, and phosphate ester salts, and having a molecular weight of 200 to 1,000.
前記脂肪酸塩は、脂肪酸の炭素数が好ましくは１０以上１８以下である。前記脂肪酸塩の具体例としては、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸及びこれらの混合物のアルカリ金属塩、有機アミン塩が挙げられる。 The fatty acid salt preferably has a carbon number of 10 or more and 18 or less. Specific examples of the fatty acid salt include alkali metal salts and organic amine salts of capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and mixtures thereof.
前記硫酸エステル塩としては、炭素数１０以上２０以下のアルキル基又はアルケニル基を有する硫酸エステルの塩が挙げられる。前記硫酸エステル塩の具体例としては、炭素数１０以上２０以下のアルキル基又はアルケニル基を有する硫酸エステル塩（ＡＳ）、ポリオキシアルキレンアルキル（又はアルケニル）エーテル硫酸エステル塩（ＡＥＳ）（例えば、炭素数２以上４以下のアルキレンオキサイドの平均付加モル数が０．５モル以上１０モル以下であり、炭素数１０以上２０以下の直鎖又は分岐鎖のアルキル基又はアルケニル基を有する、アルキル又はアルケニルエーテル硫酸エステル塩）、炭素数１０以上２０以下の直鎖又は分岐鎖のアルキル基又はアルケニル基を有するポリオキシアルキレンアルキル又はアルケニルフェニルエーテル硫酸エステル塩、ひまし油硫酸エステル塩が挙げられる。 The sulfate salts include sulfate salts having an alkyl or alkenyl group having 10 to 20 carbon atoms. Specific examples of the sulfate salts include sulfate salts having an alkyl or alkenyl group having 10 to 20 carbon atoms (AS), polyoxyalkylene alkyl (or alkenyl) ether sulfate salts (AES) (for example, alkyl or alkenyl ether sulfate salts having an average added mole number of alkylene oxide having 2 to 4 carbon atoms of 0.5 to 10 moles and having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms), polyoxyalkylene alkyl or alkenyl phenyl ether sulfate salts having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms, and castor oil sulfate salts.
前記スルホン酸塩の具体例としては、炭素数１０以上２０以下のアルカンスルホン酸塩（ＳＡＳ）、炭素数８以上１８以下のアルキル基を有する直鎖又は分岐鎖のアルキルベンゼンスルホン酸塩（ＬＡＳ或いはＡＢＳ）、炭素数１０以上２０以下のα－オレフィンスルホン酸塩（ＡＯＳ）、ジもしくは、モノアルキルスルホコハク酸塩（例えば、ジ（２－エチルヘキシル）スルホコハク酸ナトリウム（ＡＯＴ））、炭素数８以上２０以下の飽和又は不飽和α－スルホ脂肪酸又はそのメチル、エチルもしくはプロピルエステル塩が挙げられる。 Specific examples of the sulfonate include alkanesulfonates (SAS) having 10 to 20 carbon atoms, linear or branched alkylbenzenesulfonates (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms, α-olefinsulfonates (AOS) having 10 to 20 carbon atoms, di- or mono-alkylsulfosuccinates (e.g., sodium di(2-ethylhexyl)sulfosuccinate (AOT)), saturated or unsaturated α-sulfo fatty acids having 8 to 20 carbon atoms, or methyl, ethyl, or propyl ester salts thereof.
前記燐酸エステル塩としては、炭素数１０以上２０以下のアルキル基又はアルケニル基を有する燐酸エステルの塩が挙げられる。前記燐酸エステル塩の具体例としては、ポリオキシアルキレンアルキルエーテル燐酸塩、ポリオキシアルキレンアルキルフェニルエーテル燐酸塩、長鎖アルキル燐酸塩が挙げられる。前記燐酸塩としては、例えば、モノエステル体、ジエステル体、モノ体とジ体の任意の混合物（セスキエステル体）を用いることができる。 The phosphate ester salts include salts of phosphate esters having an alkyl or alkenyl group having 10 to 20 carbon atoms. Specific examples of the phosphate ester salts include polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkyl phenyl ether phosphates, and long-chain alkyl phosphates. The phosphate salts that can be used include, for example, monoesters, diesters, and any mixtures of mono- and di-esters (sesquiesters).
（Ｂ）成分としては、（Ａ）成分の浸透促進の観点から、硫酸エステル塩（ＡＳ）、ポリオキシアルキレンアルキル又はアルケニルエーテル硫酸エステル塩（ＡＥＳ）、及びアルキルベンゼンスルホン酸塩（ＬＡＳ）から選ばれる陰イオン界面活性剤が好ましい。
（Ｂ）成分としては、硫酸エステル塩（ＡＳ）、及びポリオキシアルキレンアルキル又はアルケニルエーテル硫酸エステル塩（ＡＥＳ）から選ばれる陰イオン界面活性剤が、（Ａ）成分との混合ミセル形成の観点から、更に好ましい。
As the component (B), from the viewpoint of promoting the penetration of the component (A), an anionic surfactant selected from sulfate ester salts (AS), polyoxyalkylene alkyl or alkenyl ether sulfate salts (AES), and alkylbenzene sulfonate salts (LAS) is preferred.
As the component (B), an anionic surfactant selected from sulfate ester salts (AS) and polyoxyalkylene alkyl or alkenyl ether sulfate salts (AES) is more preferred from the viewpoint of forming mixed micelles with the component (A).
（Ｂ）成分としては、アルキル硫酸エステル塩、ポリオキシエチレンアルキルエーテル硫酸エステル塩、及びアルキルベンゼンスルホン酸塩から選ばれる、分子量２００以上１０００以下の陰イオン界面活性剤が好ましく、アルキル硫酸エステル塩、及びポリオキシエチレンアルキルエーテル硫酸エステル塩から選ばれる、分子量２００以上１０００以下の陰イオン界面活性剤が、混合ミセル形成による石油系化合物への（Ａ）成分の浸透促進の観点から、より好ましい。 As component (B), an anionic surfactant having a molecular weight of 200 to 1000 selected from alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, and alkylbenzene sulfonates is preferred, and an anionic surfactant having a molecular weight of 200 to 1000 selected from alkyl sulfate ester salts and polyoxyethylene alkyl ether sulfate ester salts is more preferred from the viewpoint of promoting the penetration of component (A) into petroleum-based compounds by forming mixed micelles.
アルキル硫酸エステル塩は、（Ａ）成分との混合ミセル形成の観点から、アルキル基の炭素数が１０以上１８以下であるアルキル硫酸エステル塩が好ましい。
ポリオキシエチレンアルキルエーテル硫酸エステル塩は、（Ａ）成分との混合ミセル形成の観点から、アルキル基の炭素数が１０以上１８以下であり、エチレンオキシドの平均付加モル数が０．５以上５．０以下のポリオキシエチレンアルキルエーテル硫酸エステル塩が好ましい。
アルキルベンゼンスルホン酸は、混合ミセル形成による石油系化合物への（Ａ）成分の浸透促進の観点から、アルキル基の炭素数が１０以上１４以下であるアルキルベンゼンスルホン酸塩が好ましい。
From the viewpoint of forming mixed micelles with the component (A), the alkyl sulfate is preferably an alkyl sulfate having an alkyl group having 10 or more and 18 or less carbon atoms.
From the viewpoint of forming mixed micelles with the component (A), the polyoxyethylene alkyl ether sulfate is preferably a polyoxyethylene alkyl ether sulfate in which the alkyl group has 10 or more and 18 or less carbon atoms and the average number of moles of ethylene oxide added is 0.5 or more and 5.0 or less.
From the viewpoint of promoting the penetration of component (A) into petroleum-based compounds by forming mixed micelles, the alkylbenzenesulfonate is preferably an alkylbenzenesulfonate having an alkyl group with 10 or more and 14 or less carbon atoms.
（Ｂ）成分の陰イオン界面活性剤の塩は、アルカリ金属塩、アルカリ土類金属塩、アミン塩、アンモニウム塩、アルカノールアミン塩などが挙げられる。塩は、水和度による混合ミセル形成の観点から、アルカリ金属塩及びアルカノールアミン塩から選ばれる塩が好ましく、ナトリウム塩又はアルカノールアミン塩がより好ましい。アルカノールアミン塩は、炭素数１以上３以下のアルカノール基を１以上３以下有するアルカノールアミンの塩が好ましい。 Examples of salts of the anionic surfactant of component (B) include alkali metal salts, alkaline earth metal salts, amine salts, ammonium salts, and alkanolamine salts. From the viewpoint of mixed micelle formation depending on the degree of hydration, the salt is preferably a salt selected from alkali metal salts and alkanolamine salts, and more preferably a sodium salt or an alkanolamine salt. The alkanolamine salt is preferably a salt of an alkanolamine having 1 to 3 alkanol groups with 1 to 3 carbon atoms.
（Ｂ）成分は、（Ａ）成分との混合ミセル形成による曇点向上の観点から、デイビス法によるＨＬＢが、１０以上、更に１２以上であることが好ましく、そして、（Ａ）成分の浸透により改質された石油系化合物の洗浄性（乳化性）の観点から、４０以下、更に３５以下であることが好ましい。なお、本発明では、（Ｂ）成分のＨＬＢは、塩をナトリウム塩に置き換えた化合物に基づいて計算した値を採用する。その際、（Ｂ）成分が多量体型の塩、例えば脂肪酸のアルカリ土類金属塩などの化合物である場合は、当該化合物を構成する単量体のナトリウム塩をその化合物のＨＬＢとする。 From the viewpoint of improving the cloud point by forming mixed micelles with component (A), component (B) preferably has an HLB of 10 or more, more preferably 12 or more, as determined by the Davis method, and from the viewpoint of the cleaning properties (emulsifying properties) of the petroleum-based compound modified by the penetration of component (A), it is preferably 40 or less, more preferably 35 or less. In the present invention, the HLB of component (B) is a value calculated based on a compound in which the salt is replaced with a sodium salt. In this case, when component (B) is a compound such as a polymeric salt, for example an alkaline earth metal salt of a fatty acid, the sodium salt of the monomer that constitutes the compound is taken as the HLB of that compound.
本発明では、（Ａ）成分と（Ｂ）成分の混合ミセル形成による洗浄性向上の観点から、（Ｂ）成分がアルキル基又はアルケニル基を有し、（Ａ）成分のアルキル基又はアルケニル基の炭素数と、（Ｂ）成分のアルキル基又はアルケニル基の炭素数との差が４以内、更に２以内、更に１以内であることが好ましい。更に（Ａ）成分のアルキル基又はアルケニル基の炭素数と（Ｂ）成分のアルキル基又はアルケニル基の炭素数との差が０、すなわち、両者の炭素数が同じであってもよい。 In the present invention, from the viewpoint of improving the cleaning properties by forming mixed micelles of components (A) and (B), it is preferable that component (B) has an alkyl group or an alkenyl group, and the difference between the carbon number of the alkyl group or the alkenyl group of component (A) and the carbon number of the alkyl group or the alkenyl group of component (B) is 4 or less, further preferably 2 or less, further preferably 1 or less. Furthermore, the difference between the carbon number of the alkyl group or the alkenyl group of component (A) and the carbon number of the alkyl group or the alkenyl group of component (B) may be 0, that is, the number of carbon atoms of both may be the same.
〔組成、任意成分等〕
本発明の土壌用洗浄剤組成物は、石油系化合物の乳化による洗浄性向上の観点から、（Ａ）成分を、好ましくは３質量％以上、より好ましくは５質量％以上、更に好ましくは７質量％以上、そして、好ましくは３０質量％以下、より好ましくは２０質量％以下、更に好ましくは１５質量％以下含有する。
[Composition, optional ingredients, etc.]
From the viewpoint of improving cleaning properties by emulsifying petroleum-based compounds, the soil cleaner composition of the present invention contains component (A) in an amount of preferably 3 mass % or more, more preferably 5 mass % or more, even more preferably 7 mass % or more, and preferably 30 mass % or less, more preferably 20 mass % or less, even more preferably 15 mass % or less.
本発明の土壌用洗浄剤組成物は、石油系化合物を落としやすい状態に改質する観点から、（Ｂ）成分を、０．３質量％以上、より好ましくは０．５質量％以上、そして、好ましくは８質量％以下、より好ましくは５質量％以下、更に好ましくは３質量％以下含有する。 The soil cleaner composition of the present invention contains component (B) in an amount of 0.3% by mass or more, more preferably 0.5% by mass or more, and preferably 8% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, in order to modify the soil so that petroleum-based compounds are easily removed.
本発明の土壌用洗浄剤組成物は、（Ａ）成分の含有量と（Ｂ）成分の含有量の合計に対する（Ｂ）成分の含有量の比率である（Ｂ）／〔（Ａ）＋（Ｂ）〕が、石油系化合物を落としやすい状態に改質する観点から、３質量％以上、好ましくは５質量％以上、より好ましくは８質量％以上、更に改質された石油系化合物の乳化による洗浄性向上の観点から、そして、２５質量％以下、好ましくは２０質量％以下、より好ましくは１８質量％以下である。 In the soil cleaner composition of the present invention, the ratio of the content of the (B) component to the total content of the (A) component and the (B) component, (B)/[(A)+(B)], is 3% by mass or more, preferably 5% by mass or more, more preferably 8% by mass or more, from the viewpoint of modifying petroleum-based compounds to a state in which they are easily removed, and from the viewpoint of improving the cleaning properties by emulsifying the modified petroleum-based compounds, is 25% by mass or less, preferably 20% by mass or less, more preferably 18% by mass or less.
本発明の土壌用洗浄剤組成物は、（Ａ）成分、（Ｂ）成分以外の界面活性剤を含有することもできる。本発明の土壌用洗浄剤組成物は、全界面活性剤中、（Ａ）成分及び（Ｂ）成分の合計の割合は、好ましくは９０質量％以上、より好ましくは９５質量％以上、そして、好ましくは１００質量％以下であり、１００質量％であってもよい。 The soil cleaning composition of the present invention may also contain surfactants other than the components (A) and (B). In the soil cleaning composition of the present invention, the total proportion of the components (A) and (B) in the total surfactants is preferably 90% by mass or more, more preferably 95% by mass or more, and preferably 100% by mass or less, and may be 100% by mass.
本発明の土壌用洗浄剤組成物は、本発明の効果を損なわない範囲内で、その他の任意成分を、目的に応じて適宜含有することができる。 The soil cleaning composition of the present invention may contain other optional ingredients as appropriate depending on the purpose, as long as the effects of the present invention are not impaired.
また、本発明の土壌洗浄剤組成物は、ゲル化防止剤、増粘剤、香料、染料、顔料、殺菌剤、防腐剤、ｐＨ調整剤などの成分を含有することができる。 The soil cleaning agent composition of the present invention may also contain ingredients such as anti-gelling agents, thickeners, fragrances, dyes, pigments, bactericides, preservatives, and pH adjusters.
本発明の土壌用洗浄剤組成物は、水を含有することができる。水は、組成物の残部であってよく、例えば、組成物中の水の含有量は、１０質量％以上９０質量％以下である。 The soil cleaning composition of the present invention may contain water. The water may be the remainder of the composition, and for example, the water content in the composition is 10% by mass or more and 90% by mass or less.
本発明の土壌用洗浄剤組成物は、複合汚染として想定される重金属等の土壌からの溶出の観点から、２０℃のｐＨが、好ましくは６以上、より好ましくは６．５以上、そして、好ましくは８以下、より好ましくは７．５以下である。 The soil cleaning composition of the present invention has a pH at 20°C of preferably 6 or more, more preferably 6.5 or more, and preferably 8 or less, more preferably 7.5 or less, from the viewpoint of preventing the elution of heavy metals and other contaminants from the soil, which are assumed to be complex contaminants.
本発明の土壌用洗浄剤組成物は、曇点が好ましくは４０℃以上、より好ましくは５０℃以上、更に好ましくは６０℃以上である。本発明の土壌用洗浄剤組成物は、曇点よりも低い温度で洗浄する方が、洗浄力がより効果的に発現すると考えられる。そのため、曇点が高くなれば洗浄力が発現する温度領域は拡張される。すなわち、曇点が前記の範囲であると、低温から高温での洗浄で良好な洗浄力が得られるため、より有利である。なお、曇点は、（Ａ）成分を、０．２質量％含有する組成物について測定されたものであってよい。本発明の土壌用洗浄剤組成物は、（Ａ）成分を０．２質量％含有する組成での曇点が好ましくは４０℃以上であってよい。 The soil cleaning composition of the present invention preferably has a cloud point of 40°C or higher, more preferably 50°C or higher, and even more preferably 60°C or higher. It is believed that the soil cleaning composition of the present invention exhibits cleaning power more effectively when it is used for cleaning at a temperature lower than the cloud point. Therefore, the temperature range in which cleaning power is exhibited is expanded as the cloud point increases. In other words, it is more advantageous for the cloud point to be within the above range, since good cleaning power can be obtained by cleaning at low to high temperatures. The cloud point may be measured for a composition containing 0.2% by mass of component (A). The soil cleaning composition of the present invention may preferably have a cloud point of 40°C or higher for a composition containing 0.2% by mass of component (A).
本発明の土壌用洗浄剤組成物は、石油系化合物により汚染された土壌を洗浄するものである。すなわち、本発明は、土壌中の、石油系化合物のような油性汚れを洗浄するものである。石油系化合物は、例えば、石油系炭化水素が挙げられる。石油系化合物は、例えば、ガソリン、灯油、軽油、重油、機械油などであってよい。 The soil cleaning composition of the present invention is for cleaning soil contaminated with petroleum-based compounds. That is, the present invention is for cleaning oily stains such as petroleum-based compounds in soil. Examples of petroleum-based compounds include petroleum-based hydrocarbons. Examples of petroleum-based compounds may be gasoline, kerosene, light oil, heavy oil, machine oil, etc.
本発明の土壌用洗浄剤組成物は、細粒土に対しての油性汚れ洗浄用であってよい。ここで、細粒土とは、粒径０．０７５ｍｍ以下の土壌であってよい。掘削土壌などの土壌の粒径は、粒径０．０７５ｍｍ以下などの土壌を対象とした試験方法であるＪＩＳ Ａ１２０４「土の粒度試験方法」等によって測定される。 The soil cleaning composition of the present invention may be used for cleaning oily dirt from fine-grained soil. Here, fine-grained soil may be soil with a particle size of 0.075 mm or less. The particle size of soil such as excavated soil is measured by JIS A1204 "Soil Particle Size Test Method", which is a test method for soil with a particle size of 0.075 mm or less.
本発明の土壌用洗浄剤組成物は、（Ａ）成分と、（Ｂ）成分と、水とを配合してなり、（Ａ）成分の配合量と（Ｂ）成分の配合量の合計に対する（Ｂ）成分の配合量の比率である（Ｂ）／〔（Ａ）＋（Ｂ）〕が３質量％以上２５質量％以下である、石油系化合物により汚染された土壌を洗浄する、土壌用洗浄剤組成物であってよい。前記した好ましい態様はこの土壌用洗浄剤組成物に適宜適用できる。また、前記した各成分の含有量は、配合量に置き換えてこの土壌用洗浄剤組成物に適用できる。 The soil cleaner composition of the present invention may be a soil cleaner composition for cleaning soil contaminated by petroleum compounds, which is a mixture of component (A), component (B), and water, and in which the ratio of the amount of component (B) to the total amount of component (A) and component (B), (B)/[(A)+(B)], is 3% by mass or more and 25% by mass or less. The above-mentioned preferred embodiments can be appropriately applied to this soil cleaner composition. In addition, the contents of each of the above-mentioned components can be applied to this soil cleaner composition by replacing them with the amounts of the components.
＜多剤型土壌用洗浄剤＞
本発明は、（Ａ）成分を含有する剤（Ａ）と、（Ｂ）成分を含有する剤（Ｂ）とを含む多剤型土壌用洗浄剤であって、
剤（Ａ）及び剤（Ｂ）の少なくとも一方が水を含有し、
剤（Ａ）と剤（Ｂ）とを混合して、（Ａ）成分の含有量と（Ｂ）成分の含有量の合計に対する（Ｂ）成分の含有量の比率である（Ｂ）／〔（Ａ）＋（Ｂ）〕が３質量％以上２５質量％以下である、石油系化合物により汚染された土壌を洗浄する土壌用洗浄剤組成物を調製するために用いられる、
多剤型土壌用洗浄剤を提供する。
本発明の多剤型土壌用洗浄剤には、本発明の土壌用洗浄剤組成物で述べた事項を適宜適用することができる。例えば、本発明の多剤型土壌用洗浄剤における（Ａ）成分、（Ｂ）成分の具体例や好ましい態様などは、本発明の土壌用洗浄剤組成物と同じである。
<Multi-agent soil cleaner>
The present invention relates to a multi-agent type soil washing agent comprising an agent (A) containing an (A) component and an agent (B) containing an (B) component,
At least one of the agent (A) and the agent (B) contains water;
The agent (A) and the agent (B) are mixed to prepare a soil washing agent composition for washing soil contaminated by petroleum-based compounds, in which the ratio of the content of the (B) component to the total content of the (A) component and the (B) component, that is, (B)/[(A)+(B)], is 3 mass% or more and 25 mass% or less.
A multi-agent soil cleaner is provided.
The matters described in the soil washing composition of the present invention can be appropriately applied to the multi-agent soil washing agent of the present invention. For example, specific examples and preferred aspects of the components (A) and (B) in the multi-agent soil washing agent of the present invention are the same as those in the soil washing composition of the present invention.
剤（Ａ）と剤（Ｂ）は、土壌の洗浄の際に混合され、所定の土壌用洗浄剤組成物が調製される。
本発明の多剤型土壌用洗浄剤は、本発明の土壌用洗浄剤組成物の調製に好適に用いられる。
The agents (A) and (B) are mixed when washing the soil to prepare a predetermined soil washing agent composition.
The multi-formula soil cleaner of the present invention is suitably used for preparing the soil cleaner composition of the present invention.
剤（Ａ）は、（Ａ）成分を、５０質量％以上、更に８０質量％以上、更に９０質量％以上、そして、１００質量％以下含有することが好ましく、１００質量％含有してもよい。
また、剤（Ｂ）は、（Ｂ）成分を、２０質量％以上、更に３０質量％以上、そして、１００質量％以下含有することが好ましく、１００質量％含有してもよい。
The agent (A) preferably contains 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and still more preferably 100% by mass or less of the (A) component, and may contain 100% by mass.
The agent (B) preferably contains 20% by mass or more, more preferably 30% by mass or more, and still more preferably 100% by mass or less of the (B) component, and may contain 100% by mass.
本発明では、（Ａ）成分と（Ｂ）成分が別の剤に配合されていることが好ましい。剤（Ａ）は（Ｂ）成分を含まないものが好ましい。また、剤（Ｂ）は（Ａ）成分を含まないものが好ましい。剤（Ａ）、剤（Ｂ）は、それぞれ、前記した任意成分を含有することができる。また、本発明の多剤型土壌用洗浄剤は、（Ａ）成分も（Ｂ）成分も含まない、（Ａ）、剤（Ｂ）以外の剤を含むことができる。 In the present invention, it is preferable that the components (A) and (B) are blended in separate agents. It is preferable that the agent (A) does not contain the component (B). Also, it is preferable that the agent (B) does not contain the component (A). The agents (A) and (B) can each contain the optional components described above. Also, the multi-agent soil cleaner of the present invention can contain agents other than (A) and (B) that do not contain either the component (A) or the component (B).
本発明の多剤型土壌用洗浄剤は、１つ１つの剤が独立した物品となっている形態（例えばキットなど）や、１つ１つの剤が相互に混合されない状態で１つの物品にまとめて収容されている形態（例えば２剤型洗浄剤物品など）など、種々の形態であってよい。 The multi-agent soil cleaner of the present invention may be in various forms, such as a form in which each agent is an independent item (e.g., a kit, etc.), or a form in which each agent is contained together in a single item without being mixed with each other (e.g., a two-agent cleaner item, etc.).
＜掘削土壌の洗浄方法＞
本発明は、石油系化合物により汚染された掘削土壌を、（Ａ）成分と、（Ｂ）成分と、水とを用いて洗浄する、掘削土壌の洗浄方法であって、
（Ａ）成分と（Ｂ）成分とを、（Ａ）成分と（Ｂ）成分との合計に対する（Ｂ）成分の比率である（Ｂ）／〔（Ａ）＋（Ｂ）〕が３質量％以上２５質量％以下となるように用いる、掘削土壌の洗浄方法を提供する。
本発明の掘削土壌の洗浄方法には、本発明の土壌用洗浄剤組成物で述べた事項を適宜適用することができる。例えば、本発明の掘削土壌の洗浄方法における（Ａ）成分、（Ｂ）成分の具体例や好ましい態様などは、本発明の土壌用洗浄剤組成物と同じである。本発明の掘削土壌の洗浄方法には、本発明の土壌用洗浄剤組成物又は本発明の多剤型土壌用洗浄剤を用いることができる。
<How to wash excavated soil>
The present invention relates to a method for washing excavated soil, comprising washing excavated soil contaminated with petroleum compounds using component (A), component (B), and water, the method comprising the steps of:
The present invention provides a method for washing excavated soil, in which component (A) and component (B) are used in such a manner that the ratio of component (B) to the total of components (A) and (B), that is, (B)/[(A)+(B)], is 3% by mass or more and 25% by mass or less.
The matters described in the soil washing composition of the present invention can be appropriately applied to the method for washing excavated soil of the present invention. For example, specific examples and preferred aspects of the (A) component and the (B) component in the method for washing excavated soil of the present invention are the same as those in the soil washing composition of the present invention. The method for washing excavated soil of the present invention can use the soil washing composition of the present invention or the multi-agent soil washing agent of the present invention.
本発明の掘削土壌の洗浄方法では、掘削土壌と水とを混合し、これに（Ａ）成分と（Ｂ）成分とを混合することができる。
本発明の掘削土壌の洗浄方法では、掘削土壌と水とを混合して、比重が好ましくは１．０５以上、より好ましくは１．１８以上、そして、好ましくは１．４０以下、より好ましくは１．２５以下の混合物を調製し、この混合物に、（Ａ）成分と（Ｂ）成分とを混合することができる。
本発明の掘削土壌の洗浄方法では、（Ａ）成分を、掘削土壌と水との混合物に対して、洗浄性の観点から、好ましくは０．０４質量％以上、より好ましくは０．０５質量％以上、より更に好ましくは０．１質量％以上、そして、経済性の観点から好ましくは０．４質量％以下、より好ましくは０．３質量％以下、より更に好ましくは０．２質量％以下用いることができる。
本発明の掘削土壌の洗浄方法では、（Ｂ）成分を、掘削土壌と水との混合物に対して、好ましくは０．０１質量％以上、より好ましくは０．０１５質量％以上、そして、好ましくは０．１質量％以下用いることができる。
本発明の掘削土壌の洗浄方法では、（Ａ）成分と（Ｂ）成分を合計で、掘削土壌と水との混合物に対して、好ましくは０．０５質量％以上、より好ましくは０．０６質量％以上、そして、好ましくは０．５質量％以下、より好ましくは０．３質量％以下、より更に好ましくは０．２質量％以下用いることができる。
In the method for washing excavated soil of the present invention, the excavated soil is mixed with water, and then component (A) and component (B) can be mixed with the mixture.
In the method for washing excavated soil of the present invention, the excavated soil is mixed with water to prepare a mixture having a specific gravity of preferably 1.05 or more, more preferably 1.18 or more, and preferably 1.40 or less, more preferably 1.25 or less, and this mixture can be mixed with component (A) and component (B).
In the method for washing excavated soil of the present invention, the amount of component (A) can be preferably 0.04 mass % or more, more preferably 0.05 mass % or more, and even more preferably 0.1 mass % or more, based on the mixture of excavated soil and water from the viewpoint of washability, and from the viewpoint of economy, preferably 0.4 mass % or less, more preferably 0.3 mass % or less, and even more preferably 0.2 mass % or less.
In the method for washing excavated soil of the present invention, component (B) can be used in an amount of preferably 0.01 mass % or more, more preferably 0.015 mass % or more, and preferably 0.1 mass % or less, based on the mixture of excavated soil and water.
In the method for washing excavated soil of the present invention, the total amount of components (A) and (B) can be used in an amount of preferably 0.05 mass% or more, more preferably 0.06 mass% or more, and preferably 0.5 mass% or less, more preferably 0.3 mass% or less, and even more preferably 0.2 mass% or less, based on the mixture of excavated soil and water.
本発明の掘削土壌の洗浄方法では、洗浄を、洗浄性の効率化の観点から、好ましくは２回以上、より好ましくは３回以上、そして、回収水処理の観点から、好ましくは５回以下行うことができる。 In the method for washing excavated soil of the present invention, washing can be performed preferably two or more times, more preferably three or more times, from the viewpoint of efficient washing, and preferably five or less times, from the viewpoint of treatment of recovered water.
本発明の掘削土壌の洗浄方法では、洗浄した掘削土壌のすすぎは行ってもよいし、行わなくてもよい。工程の簡略化などの観点では、本発明では、すすぎ工程を実施しなくてもよい。 In the method for washing excavated soil of the present invention, rinsing of the washed excavated soil may or may not be performed. From the viewpoint of simplifying the process, the present invention does not require a rinsing step.
本発明の掘削土壌の洗浄方法では、掘削土壌を、その土壌が存在する場所（現地）で洗浄してもよいし、原位置とは異なる場所（現地外）で洗浄してもよい。例えば、掘削土壌を、現地とは異なる場合に設けた洗浄設備で洗浄することができる。その際、例えば、現地から掘削により採取した土壌を、現地とは異なる場所に設けた洗浄設備に移送して洗浄することができる。洗浄設備は、現地の近くに設置することが好ましい。例えば、ある区域内の所定の場所（現地）で土壌を採取し、同じ区域内の採取場所とは別の場所に洗浄設備を設けることができる。このように、いわゆる現地プラントとして洗浄設備を設けて掘削土壌を洗浄することができる。 In the method for washing excavated soil of the present invention, the excavated soil may be washed at the location where the soil exists (on-site), or at a location other than the original location (off-site). For example, the excavated soil can be washed in washing equipment installed at a location other than the on-site. In this case, for example, soil collected by excavation from the on-site can be transported to washing equipment installed at a location other than the on-site and washed. It is preferable to install the washing equipment near the on-site. For example, soil can be collected at a specified location (on-site) within a certain area, and the washing equipment can be installed at a location other than the collection location within the same area. In this way, the excavated soil can be washed by installing washing equipment as a so-called on-site plant.
本発明の掘削土壌の洗浄方法では、（Ａ）成分、（Ｂ）成分及び水を含有するｐＨ６以上８以下の混合物を掘削土壌に混合することができる。該混合物は、本発明の土壌用洗浄剤組成物又はその水による希釈物であってよい。該混合物における（Ａ）成分と（Ｂ）成分の含有量は特に限定は無いが、（Ｂ）／〔（Ａ）＋（Ｂ）〕の質量比が３質量％以上２５質量％以下であることが好ましい。該混合物は、必要に応じて（Ａ）成分、（Ｂ）成分以外の成分を含有していてもよい。 In the method for cleaning excavated soil of the present invention, a mixture containing component (A), component (B), and water and having a pH of 6 to 8 can be mixed with excavated soil. The mixture may be the soil cleaning agent composition of the present invention or a dilution thereof with water. There are no particular limitations on the contents of components (A) and (B) in the mixture, but it is preferable that the mass ratio of (B)/[(A)+(B)] is 3% by mass or more and 25% by mass or less. The mixture may contain components other than components (A) and (B) as necessary.
本発明の掘削土壌の洗浄方法では、（Ａ）成分と（Ｂ）成分を、ｐＨ６以上８以下で掘削土壌と接触させることができる。前記した、（Ａ）成分、（Ｂ）成分及び水を含有するｐＨ６以上８以下の混合物を用いることは、このような方法を行うのに好ましい。 In the method for washing excavated soil of the present invention, the components (A) and (B) can be contacted with the excavated soil at a pH of 6 to 8. It is preferable to use the mixture containing the components (A), (B), and water and having a pH of 6 to 8 inclusive for carrying out such a method.
本発明の掘削土壌の洗浄方法では、洗浄後、土壌を遠心分離することが好ましい。遠心分離の条件は、例えば、遠心加速度が１００Ｇ以上１２００Ｇ以下、処理時間が１分以上１０分以下である。遠心分離により、土壌と液相との分離が促進され、土壌の回収、再利用（埋め戻し）が容易となる。 In the method for washing excavated soil of the present invention, it is preferable to centrifuge the soil after washing. The conditions for centrifugation are, for example, a centrifugal acceleration of 100 G or more and 1200 G or less, and a treatment time of 1 minute or more and 10 minutes or less. Centrifugation promotes separation of the soil and the liquid phase, making it easier to recover and reuse (backfill) the soil.
洗浄後の土壌は、採取した場所や別の場所に埋め戻して再利用することができる。 After cleaning, the soil can be reused by backfilling it in the area where it was collected or in another location.
表１～３に示す土壌用洗浄剤組成物を調製し、以下方法で洗浄試験と曇点の測定を行った。結果を表１～３に示す。 The soil cleaning compositions shown in Tables 1 to 3 were prepared, and cleaning tests and cloud point measurements were performed using the following methods. The results are shown in Tables 1 to 3.
（１）洗浄試験
（１－１）評価用の模擬油汚染細粒土の調製
土木用微粉末粘土（スミクレー、住友大阪セメント株式会社）４００ｇと、軽油６．２ｇとを、ハンドミキサーで均一になるように撹拌し、模擬油汚染細粒土を調製した。なお、ここで用いた前記土木用微粉末粘土は、粒径０．０７５ｍｍ以下の細粒分が９０質量％以上であった。
(1) Cleaning test (1-1) Preparation of simulated oil-contaminated fine soil for evaluation 400 g of fine powdered clay for civil engineering (Sumiclair, Sumitomo Osaka Cement Co., Ltd.) and 6.2 g of light oil were mixed uniformly with a hand mixer to prepare simulated oil-contaminated fine soil. The fine powdered clay for civil engineering used here had a fine particle content of 0.075 mm or less in particle size of 90% by mass or more.
（１－２）模擬油汚染細粒土の洗浄
１００ｍｌ三角フラスコに、模擬油汚染細粒土１６．７ｇと水８３．３ｇとを投入して比重１．２の混合物を調製した。この三角フラスコに、更に表に示す土壌用洗浄剤組成物を、模擬油汚染細粒土と水の混合物に対する（Ａ）成分と（Ｂ）成分の合計が表に示す量となるように、添加後、マグネティックスターラーで３０分間撹拌した。ここで、土壌用洗浄剤組成物は、（Ａ）成分と（Ｂ）成分とを合計で１０質量％含有し、残部が水の組成物であった。表中の実施例の土壌用洗浄剤組成物は、いずれも、２０℃のｐＨが６以上８以下の範囲にあった。また、表中、（Ａ）成分のＨＬＢはグリフィン法によるＨＬＢであり、（Ｂ）成分のＨＬＢはデイビス法によるＨＬＢである。なお、（Ｂ）成分のＨＬＢは、塩をナトリウム塩に置き換えた化合物に基づいて計算した。また、なお、表には、（Ａ）成分、（Ｂ）成分に該当しない化合物も、便宜的にそれらの欄に示した。
３０分後、撹拌を止め、混合物を５０ｍｌビオラモ遠沈管２本に分け、株式会社コクサン製多本架遠心機Ｈ－８０Ｆで、１０００Ｇで５分間、遠心分離をした。
遠心終了後、上澄液分を排出し、残っている沈殿物（粘土分）に上澄液分の質量分の水を加えて、１００ｍｌ三角フラスコに移した。これを１回の洗浄とした。２回以上洗浄する場合は、１回目の洗浄後に三角フラスコに移した混合物を２回目の洗浄対象とし、以下同様の洗浄を繰り返し行った。
(1-2) Washing of simulated oil-contaminated fine soil 16.7 g of simulated oil-contaminated fine soil and 83.3 g of water were added to a 100 ml Erlenmeyer flask to prepare a mixture with a specific gravity of 1.2. The soil cleaner composition shown in the table was added to the Erlenmeyer flask so that the total amount of the (A) component and the (B) component relative to the mixture of the simulated oil-contaminated fine soil and water was the amount shown in the table, and then stirred with a magnetic stirrer for 30 minutes. Here, the soil cleaner composition contained 10 mass% of the (A) component and the (B) component in total, and the remainder was water. The soil cleaner compositions of the examples in the table all had a pH at 20°C in the range of 6 to 8. In addition, in the table, the HLB of the (A) component is the HLB according to the Griffin method, and the HLB of the (B) component is the HLB according to the Davis method. The HLB of the (B) component was calculated based on a compound in which the salt was replaced with a sodium salt. For the sake of convenience, compounds that do not fall under component (A) or component (B) are also shown in the corresponding columns in the table.
After 30 minutes, the stirring was stopped, and the mixture was divided into two 50 ml Violamo centrifuge tubes and centrifuged at 1000 G for 5 minutes in a multi-rack centrifuge H-80F manufactured by Kokusan Co., Ltd.
After centrifugation, the supernatant was discharged, and the remaining precipitate (clay) was mixed with water in an amount equal to the mass of the supernatant and transferred to a 100 ml Erlenmeyer flask. This was counted as one wash. When washing was performed twice or more times, the mixture transferred to the Erlenmeyer flask after the first wash was used as the second wash, and the same washes were repeated thereafter.
（１－３）洗浄性の評価
１． （１－２）の洗浄試験で、最終の洗浄後に遠心分離して得られた沈殿物を１００ｍｌスクリュー管に１０．０ｇ計量し、蓋をしない状態で４０℃恒温槽に１５時間入れた。並行して、前記沈殿物を約３ｇ精秤し、１０５℃恒温槽に１５時間入れ、沈殿物中の粘土分を測定した。
２． １５時間後、前記スクリュー管に、無水硫酸ナトリウムを約５０ｇ添加し振とうした。
３． 更に、前記スクリュー管に、５０ｍｌのジクロロメタンを添加し、ペンシルミキサーで１分間撹拌し、６０分静置した。
４． 静置後の上澄液を１００ｍｌメスフラスコに移し、更に３０ｍｌのジクロロメタンを添加し、ペンシルミキサーで１分間撹拌し、６０分静置した。
５． 前記４．で静置後の上澄液を、別の１００ｍｌメスフラスコに移し、更に３０ｍｌのジクロロメタンを添加し、ペンシルミキサーで１分間撹拌し、６０分静置した。
６． 前記５．で静置後の上澄液を、別の１００ｍｌメスフラスコに移し、ジクロロメタンで１００ｍｌまでメスアップしてジクロロメタン抽出液とした。
７． ジクロロメタン抽出液を０．４５μｍのフィルターでろ過後、アジレント・テクノロジー社製６８５０Ａガスクロマトグラフィーで軽油分を定量した。
８． 定量結果を沈殿物中の粘土分（１０５℃乾燥）に含まれる量に換算して残存軽油量とした。表には、土壌１ｋｇあたりの軽油分量ｍｇを、ＴＰＨ（ｍｇ／ｋｇ）として示した。
(1-3) Evaluation of cleaning properties 1. In the cleaning test (1-2), 10.0 g of the precipitate obtained by centrifugation after the final cleaning was weighed into a 100 ml screw tube and placed in a 40°C thermostatic chamber without a lid for 15 hours. In parallel, about 3 g of the precipitate was precisely weighed and placed in a 105°C thermostatic chamber for 15 hours, and the clay content in the precipitate was measured.
2. After 15 hours, about 50 g of anhydrous sodium sulfate was added to the screw tube and shaken.
3. Furthermore, 50 ml of dichloromethane was added to the screw tube, stirred with a pencil mixer for 1 minute, and allowed to stand for 60 minutes.
4. After standing, the supernatant was transferred to a 100 ml measuring flask, and 30 ml of dichloromethane was added thereto. The mixture was stirred with a pencil mixer for 1 minute and then allowed to stand for 60 minutes.
5. The supernatant liquid after leaving in step 4 above was transferred to another 100 ml measuring flask, and 30 ml of dichloromethane was added thereto. The mixture was stirred with a pencil mixer for 1 minute and left to stand for 60 minutes.
6. The supernatant liquid after leaving in step 5 above was transferred to another 100 ml measuring flask and diluted with dichloromethane to 100 ml to prepare a dichloromethane extract.
7. The dichloromethane extract was filtered through a 0.45 μm filter, and the light oil content was quantified using an Agilent Technologies 6850A gas chromatograph.
8. The quantitative results were converted into the amount contained in the clay content in the sediment (dried at 105°C) to obtain the amount of residual light oil. In the table, the amount of light oil (mg) per kg of soil is shown as TPH (mg/kg).
（２）土壌用洗浄剤組成物の曇点
表に示す（Ａ）成分と（Ｂ）成分を（Ｂ）／〔（Ａ）＋（Ｂ）〕で且つ合計で０．２質量％含有し、残部が水である土壌用洗浄剤組成物を調製した。
土壌用洗浄剤組成物２０ｇを、３０ｍｌのスクリュー管に投入し、ふたをした状態で、２０℃恒温槽に１時間入れた。
１時間後、外観を目視で観察し、白濁している場合は、曇点２０℃以下として試験を終了し、透明である場合は、更に３０℃恒温槽に１時間入れて試験を継続した。この評価を１０℃毎に７０℃まで行い、白濁してくる温度を確認した。７０℃でも白濁しない場合は、表には「７０℃以上」と記載した。
(2) Cloud point of soil cleaner composition Soil cleaner compositions were prepared containing the components (A) and (B) shown in the table in a ratio of (B)/[(A)+(B)] in a total amount of 0.2 mass%, with the remainder being water.
20 g of the soil cleaning composition was placed in a 30 ml screw tube, which was then placed in a thermostatic chamber at 20° C. for 1 hour with the lid on.
After 1 hour, the appearance was visually observed, and if it was cloudy, the cloud point was set to 20°C or less and the test was terminated, whereas if it was transparent, the test was continued by placing it in a 30°C thermostatic chamber for another hour. This evaluation was performed in 10°C increments up to 70°C, and the temperature at which it became cloudy was confirmed. If it was not cloudy even at 70°C, it was recorded as "70°C or higher" in the table.
表１中、（Ａ）成分は、Ｃの次の数字はアルキル基又はアルケニル基の炭素数であり、Ｆは不飽和結合の数を示す。ｉＣ８はイソオクチル基である。ＥＯはエチレンオキシ基であり、カッコに付した数字は平均付加モル数である。例えば、Ｃ１０（ＥＯ）３は、アルキル基の炭素数が１０でエチレンオキシドの平均付加モル数が３のポリオキシエチレンアルキルエーテルを意味する（以下同様）。
また、表１中、（Ｂ）成分は、以下のものである（以下同様）。
Ｃ１２ＯＳＯ３・Ｎａ：炭素数１２のアルキル基を有するアルキル硫酸エステルのナトリウム塩
In Table 1, for component (A), the number following C is the number of carbon atoms in the alkyl or alkenyl group, and F is the number of unsaturated bonds. iC8 is an isooctyl group. EO is an ethyleneoxy group, and the number in parentheses is the average number of moles added. For example, C10(EO)3 means a polyoxyethylene alkyl ether in which the alkyl group has 10 carbon atoms and the average number of moles of ethylene oxide added is 3 (the same applies below).
In addition, in Table 1, component (B) is as follows (the same applies below).
COSO3.Na: Sodium salt of alkyl sulfate ester having an alkyl group with 12 carbon atoms
表１の結果から、(Ａ）成分と（Ｂ）成分とを、所定の比率で併用すると、土壌の洗浄性に優れた土壌用洗浄剤組成物が得られることがわかる。 The results in Table 1 show that by combining components (A) and (B) in a specified ratio, a soil cleaning composition with excellent soil cleaning properties can be obtained.
表２の結果から、実施例２－１では、洗浄温度が２０℃でも５０℃でも良好な洗浄性を示すことがわかる。一方、比較例２－１では、いずれの洗浄温度でも洗浄性が悪いことがわかる。 The results in Table 2 show that Example 2-1 exhibits good cleaning properties at cleaning temperatures of both 20°C and 50°C. On the other hand, Comparative Example 2-1 exhibits poor cleaning properties at both cleaning temperatures.
表３中、（Ｂ）成分は、以下のものである（以下同様）。
Ｃ１２ＯＳＯ３・ＴＥＡ：炭素数１２のアルキル基を有するアルキル硫酸エステルのトリエタノールアミン塩
Ｃ１２ＯＳＯ３・ＮＨ４：炭素数１２のアルキル基を有するアルキル硫酸エステルのアンモニウム塩
Ｃ１２（ＥＯ）２ＯＳＯ３・Ｎａ：炭素数１２のアルキル基を有し、エチレンオキシドの平均付加モル数が２である、ポリオキシエチレンアルキルエーテル硫酸エステルのナトリウム塩
ＬＡＳ・Ｎａ：炭素数１２のアルキル基を有するアルキルベンゼンスルホン酸のナトリウム塩
Ｃ１１ＣＯＯ・Ｎａ：炭素数１２の脂肪酸のナトリウム塩
Ｃ７ＣＯＯ・Ｎａ：炭素数８の脂肪酸のナトリウム塩
ＰＡＡ・Ｎａ：ポリアクリル酸のナトリウム塩、重量平均分子量３０００
In Table 3, component (B) is as follows (the same applies below).
C12OSO3.TEA: triethanolamine salt of alkyl sulfate having an alkyl group with 12 carbon atoms C12OSO3.NH4: ammonium salt of alkyl sulfate having an alkyl group with 12 carbon atoms C12(EO)2OSO3.Na: sodium salt of polyoxyethylene alkyl ether sulfate having an alkyl group with 12 carbon atoms and an average number of moles of ethylene oxide added of 2 LAS.Na: sodium salt of alkylbenzene sulfonic acid having an alkyl group with 12 carbon atoms C11COO.Na: sodium salt of fatty acid having 12 carbon atoms C7COO.Na: sodium salt of fatty acid having 8 carbon atoms PAA.Na: sodium salt of polyacrylic acid, weight average molecular weight 3000
表３の結果から、分子量が本発明の範囲にある陰イオン界面活性剤を(Ａ）成分と所定の比率で併用すると、土壌の洗浄性に優れた土壌用洗浄剤組成物が得られることがわかる。 The results in Table 3 show that by combining an anionic surfactant whose molecular weight falls within the range of the present invention with component (A) in a specified ratio, a soil cleaning agent composition with excellent soil cleaning properties can be obtained.
Claims (12)
剤（Ａ）及び剤（Ｂ）の少なくとも一方が水を含有し、
剤（Ａ）と剤（Ｂ）とを混合して、（Ａ）成分の含有量と（Ｂ）成分の含有量の合計に対する（Ｂ）成分の含有量の比率である（Ｂ）／〔（Ａ）＋（Ｂ）〕が３質量％以上２５質量％以下であり、全界面活性剤中、（Ａ）成分及び（Ｂ）成分の合計の割合が９０質量％以上であり、２０℃のｐＨが６以上８以下である、石油系化合物により汚染された土壌を洗浄する土壌用洗浄剤組成物を調製するために用いられる、
多剤型土壌用洗浄剤。 A multi-agent soil washing agent comprising: (A) an agent (A) containing a polyoxyethylene alkyl or alkenyl ether having an alkyl or alkenyl group with a carbon number of 10 or more and 18 or less and an average number of moles of ethylene oxide added of 3 or more and 10 or less [hereinafter referred to as component (A)]; and (B) an agent (B) containing an anionic surfactant having a molecular weight of 200 or more and 1,000 or less [hereinafter referred to as component (B)],
At least one of the agent (A) and the agent (B) contains water;
The agent (A) and the agent (B) are mixed to prepare a soil washing agent composition for washing soil contaminated with petroleum-based compounds, in which the ratio of the content of the (B) component to the total content of the (A) component and the (B) component, (B)/[(A)+(B)], is 3 mass% or more and 25 mass% or less, the total proportion of the (A) component and the (B) component in the total surfactant is 90 mass% or more, and the pH at 20°C is 6 or more and 8 or less.
A multi-purpose soil cleaner.
（Ａ）成分と（Ｂ）成分とを、（Ａ）成分と（Ｂ）成分との合計に対する（Ｂ）成分の比率である（Ｂ）／〔（Ａ）＋（Ｂ）〕が３質量％以上２５質量％以下、且つ全界面活性剤中、（Ａ）成分及び（Ｂ）成分の合計の割合が９０質量％以上となるように用い、
（Ａ）成分と（Ｂ）成分とをｐＨ６以上８以下で掘削土壌と接触させる、
掘削土壌の洗浄方法。 1. A method for washing excavated soil contaminated with petroleum compounds, comprising washing the excavated soil with (A) a polyoxyethylene alkyl or alkenyl ether having an alkyl or alkenyl group with 10 to 18 carbon atoms and an average number of moles of ethylene oxide added of 3 to 10 (hereinafter referred to as component (A)), (B) an anionic surfactant having a molecular weight of 200 to 1,000 (hereinafter referred to as component (B)), and water,
The (A) component and the (B) component are used so that the ratio of the (B) component to the total of the (A) component and the (B) component, that is, (B)/[(A)+(B)], is 3 mass% or more and 25 mass% or less , and the total proportion of the (A) component and the (B) component in the total surfactant is 90 mass% or more ,
Contacting the (A) component and the (B) component with the excavated soil at a pH of 6 to 8;
How to clean excavated soil.
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