JP6055061B1 - Powder oil coagulant and fluid oil coagulant - Google Patents
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- 239000000701 coagulant Substances 0.000 title claims abstract description 108
- 239000000843 powder Substances 0.000 title claims abstract description 49
- 239000012530 fluid Substances 0.000 title claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 68
- 230000009969 flowable effect Effects 0.000 claims abstract description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005977 Ethylene Substances 0.000 claims abstract description 20
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920006132 styrene block copolymer Polymers 0.000 claims abstract description 19
- 229920001400 block copolymer Polymers 0.000 claims abstract description 13
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000004520 water soluble gel Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000003921 oil Substances 0.000 abstract description 131
- 239000002480 mineral oil Substances 0.000 abstract description 10
- 235000010446 mineral oil Nutrition 0.000 abstract description 10
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 230000001112 coagulating effect Effects 0.000 abstract description 2
- 238000004581 coalescence Methods 0.000 abstract 1
- 238000005345 coagulation Methods 0.000 description 27
- 230000015271 coagulation Effects 0.000 description 27
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000010687 lubricating oil Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 229960005323 phenoxyethanol Drugs 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- 229940082509 xanthan gum Drugs 0.000 description 2
- 235000010493 xanthan gum Nutrition 0.000 description 2
- 239000000230 xanthan gum Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 206010053567 Coagulopathies Diseases 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000035602 clotting Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical compound C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
【課題】 鉱油、合成油、及び非水溶性有機溶剤などの多種の油類を凝固できる粉末油凝固剤の提供、及びその粉末油凝固剤を用いて、海域などの広範囲に流出した油類を凝固させるために、圧送ポンプなどを利用して拡散投下が実施可能な流動可能型油凝固剤を提供する。【解決手段】 粉粒状のスチレン・エチレン・エチレン・プロピレン・スチレンブロック共重合体と、粉粒状のスチレン・エチレン・ブチレン・スチレンブロック共重合体と、粉粒状のスチレン・エチレン・プロピレン・ブロック共重合体からなることを特徴とする粉末油凝固剤。【選択図】 なしPROBLEM TO BE SOLVED: To provide a powder oil coagulant capable of coagulating various oils such as mineral oil, synthetic oil, and water-insoluble organic solvent, and to use the powder oil coagulant for oils that have flowed out widely in the sea area. In order to solidify, a flowable type oil coagulant that can be subjected to diffusion dropping using a pressure pump or the like is provided. SOLUTION: A granular styrene / ethylene / ethylene / propylene / styrene block copolymer, a granular styrene / ethylene / butylene / styrene block copolymer, and a granular styrene / ethylene / propylene / block copolymer. A powder oil coagulant characterized by comprising a coalescence. [Selection figure] None
Description
本発明は、油類や溶剤が流出したり漏れ出した際に、迅速に凝固させて、その流出や漏出の広がりを防ぐ油凝固剤に関し、特に、鉱油、合成油、非水溶性有機溶剤などの多種の油類、或いは溶剤と、広範囲の被凝固対象物に適応可能な粉末凝固剤に関する。 The present invention relates to an oil coagulant that quickly solidifies when oils or solvents are spilled or leaked, and prevents the spread of spills or leaks, in particular, mineral oil, synthetic oil, water-insoluble organic solvent, etc. The present invention relates to a powder coagulant that can be applied to a wide range of objects to be coagulated.
鉱油、合成油、非水溶性有機溶剤等の多種の油類、或いは溶剤は、通常、その使用中に油分或いは溶剤としての性能が低下し、その利用が不可能になった際に、廃棄処分されるが、液体状のままでは、その取扱いや保管に不便であり、廃棄方法などについても環境汚染を招き易い欠点を有している。 Various oils or solvents such as mineral oil, synthetic oil, water-insoluble organic solvent, etc., are usually disposed of when their use as oil or solvent decreases and their use becomes impossible. However, in the liquid state, it is inconvenient to handle and store, and the disposal method has a drawback that it easily causes environmental pollution.
そこで、例えば、一般式Ｓ−ＥＢ−Ｓおよび／またはＳ−ＥＰ−Ｓ（式中、Ｓはポリスチレンブロックを示し、ＥＢはポリエチレン／ブチレンブロックを示す。また、ＥＰはポリエチレン／プロピレンブロックを示す。）で表される構造を有するブロック共重合体の粒状体ないし粉状体の油凝固剤が提案されている（例えば、特許文献１参照）。 Therefore, for example, general formula S-EB-S and / or S-EP-S (wherein S represents a polystyrene block, EB represents a polyethylene / butylene block, and EP represents a polyethylene / propylene block). ) Has been proposed (for example, see Patent Document 1).
また、ポリスチレンブロックとポリブタジェンブロックからなるブロック共重合物の粉体とポリノルボルネンの粉体とからなる鉱物油の吸着・凝固剤も知られている（例えば、特許文献２参照）。
さらに、ポリスチレンブロックとポリブタジェンブロックよりなるブロック共重合体の粒径が少なくとも１ｍｍ以下の粉末高分子凝固剤、水溶性ゲル液、界面活性剤、デンプン溶液及び水からなる流動型ゲル状油凝固剤が提案されている（例えば、特許文献３参照）。
Also known is a mineral oil adsorption / coagulant comprising a block copolymer powder comprising a polystyrene block and a polybutadiene block and a polynorbornene powder (see, for example, Patent Document 2).
Furthermore, a fluidized gel oil coagulation comprising a powder polymer coagulant having a particle size of at least 1 mm or less of a block copolymer comprising a polystyrene block and a polybutadiene block, a water-soluble gel solution, a surfactant, a starch solution and water. An agent has been proposed (see, for example, Patent Document 3).
しかしながら、従来の粉末油凝固剤は、鉱油及び合成油などの多種の油類、及び非水溶性有機溶剤を含む多くの油類を一剤で凝固させる事が困難であった為、多くの油類を一剤で凝固させる性能を有する粉末油凝固剤の開発が希求されていた。 However, conventional powder oil coagulants have been difficult to coagulate various oils such as mineral oil and synthetic oil and many oils including water-insoluble organic solvents in one agent. There has been a demand for the development of a powdered oil coagulant having the ability to coagulate a single agent.
本発明は、上記課題の改善を図れる鉱油、合成油、及び非水溶性有機溶剤などの多種の油類を凝固できる粉末油凝固剤を提供する。
さらに、その粉末油凝固剤を用いて、海域などの広範囲に流出した油類を凝固させるために、圧送ポンプなどを利用して拡散投下が実施可能な流動可能型油凝固剤を提供する。この油凝固剤との接触により生成する油凝固物は、吸引ポンプ等で簡単に回収されてメッシュクリーン等での濾別により、分離した水（液体成分）はそのまま放流でき、固形物（固体成分）の油凝固物は固形燃料（助撚剤）として再利用可能となる。
The present invention provides a powder oil coagulant capable of coagulating various oils such as mineral oil, synthetic oil, and water-insoluble organic solvent that can improve the above-mentioned problems.
Furthermore, the present invention provides a flowable type oil coagulant that can be subjected to diffusion dropping using a pressure pump or the like in order to coagulate oil that has flowed over a wide area such as the sea using the powdered oil coagulant. The oil coagulum produced by contact with this oil coagulant is easily recovered with a suction pump, etc., and separated by filtration with a mesh clean or the like, the separated water (liquid component) can be discharged as it is, and the solid matter (solid component) ) Can be reused as solid fuel (auxiliary twisting agent).
このような状況に鑑み、本発明における第１の発明は、粉粒状のスチレン・エチレン・エチレン・プロピレン・スチレンブロック共重合体（以下、ＳＥＥＰＳと称す）と、粉粒状のスチレン・エチレン・ブチレン・スチレンブロック共重合体（以下、ＳＥＢＳと称す）と、粉粒状のスチレン・エチレン・プロピレン・ブロック共重合体（以下、ＳＥＰと称す）からなることを特徴とする粉末油凝固剤である。 In view of such a situation, the first invention in the present invention is a powdery styrene / ethylene / ethylene / propylene / styrene block copolymer (hereinafter referred to as SEEPS) and a powdery styrene / ethylene / butylene / A powder oil coagulant comprising a styrene block copolymer (hereinafter referred to as SEBS) and a granular styrene / ethylene / propylene block copolymer (hereinafter referred to as SEP).
本発明の第２の発明は、粉粒状のスチレン・エチレン・エチレン・プロピレン・スチレンブロック共重合体を４０〜９０重量％、粉粒状のスチレン・エチレン・ブチレン・スチレンブロック共重合体を５〜３０重量％、粉粒状のスチレン・エチレン・プロピレン・ブロック共重合体を５〜３０重量％からなることを特徴とする粉末油凝固剤である。 According to a second aspect of the present invention, a granular styrene / ethylene / ethylene / propylene / styrene block copolymer is 40 to 90% by weight, and a granular styrene / ethylene / butylene / styrene block copolymer is 5 to 30%. A powdery oil coagulant comprising 5% to 30% by weight of a powdery styrene / ethylene / propylene / block copolymer.
本発明の第３の発明は、第１及び第２の発明に記載の粉末油凝固剤と水溶性ゲル液のみとからなるゲル体であることを特徴とする流動可能型油凝固剤である。 A third invention of the present invention is a flowable oil coagulant characterized in that it is a gel body comprising only the powder oil coagulant described in the first and second inventions and a water-soluble gel liquid.
本発明の第４の発明は、粉粒状のスチレン・エチレン・エチレン・プロピレン・スチレンブロック共重合体と、粉粒状のスチレン・エチレン・ブチレン・スチレンブロック共重合体と、粉粒状のスチレン・エチレン・プロピレン・ブロック共重合体とからなる粉末油凝固剤、又は、粉粒状のスチレン・エチレン・エチレン・プロピレン・スチレンブロック共重合体を４０〜９０重量％、粉粒状のスチレン・エチレン・ブチレン・スチレンブロック共重合体を５〜３０重量％、粉粒状のスチレン・エチレン・プロピレン・ブロック共重合体を５〜３０重量％からなる粉末油凝固剤と、水溶性ゲル液のみとからなるゲル体である流動可能型油凝固剤と希釈水からなるゾル状態の流動型油凝固剤であって、前記希釈水の重量が、前記流動可能型油凝固剤の重量に対し、０．７５〜２倍の重量であり、ゾル状態の流動型油凝固剤の流動性が希釈水により調製されていることを特徴とする流動型油凝固剤である。 The fourth invention of the present invention is a powdery styrene / ethylene / ethylene / propylene / styrene block copolymer, a powdery styrene / ethylene / butylene / styrene block copolymer, and a powdery styrene / ethylene / styrene / copolymer. Powder oil coagulant comprising propylene block copolymer or powdery styrene / ethylene / ethylene / propylene / styrene block copolymer 40 to 90% by weight, powdered styrene / ethylene / butylene / styrene block A flow that is a gel body consisting of a powder oil coagulant consisting of 5 to 30% by weight of a copolymer and 5 to 30% by weight of a granular styrene / ethylene / propylene / block copolymer and a water-soluble gel solution. A sol-type fluid oil coagulant comprising a flowable oil coagulant and dilution water, wherein the weight of the dilution water is the flowable oil coagulant. Weight of agent to a weight of 0.75 to 2 times, a fluidized oil coagulant fluidity of the fluidized oil coagulant sol state is characterized by being prepared by the dilution water.
本発明の粉末油凝固剤によれば、一種類の凝固剤で「鉱油」、「合成油」、及び「非水溶性有機溶剤」などの多種の油類が凝固可能となり、凝固処理作業の効率化させるばかりでなく、凝固処理費用の低減も可能とし、工業的に優れた効果を奏するものである。
さらに、その粉末油凝固剤を用いた、圧送ポンプで海域などの広範囲に流出した油類を凝固させるために、圧送ポンプなどを利用して拡散投下が実施可能な流動可能型油凝固剤によれば、この油凝固剤との接触により生成する油凝固物は、吸引ポンプ等で簡単に回収されてメッシュクリーン等での濾別により、分離した水（液体成分）はそのまま放流でき、固形物（固体成分）の油凝固物は固形燃料（助撚剤）として再利用可能となるなどの自然環境に対する影響を押え、省資源な凝固処理を提供できる工業的に優れた効果を奏するものである。
According to the powder oil coagulant of the present invention, various kinds of oils such as “mineral oil”, “synthetic oil”, and “water-insoluble organic solvent” can be coagulated with one kind of coagulant, and the efficiency of the coagulation treatment work In addition, the coagulation treatment cost can be reduced and an industrially excellent effect can be obtained.
Furthermore, in order to coagulate oil that has flowed over a wide area such as the sea area with a pressure pump using the powder oil coagulant, a flowable type oil coagulant that can be subjected to diffusion dropping using a pressure pump or the like is used. For example, the oil coagulated product produced by contact with the oil coagulant can be easily recovered with a suction pump or the like, and the separated water (liquid component) can be discharged as it is by filtration with a mesh clean or the like. The solid component (oil coagulated product) exerts an industrially excellent effect of suppressing the influence on the natural environment such as being reusable as a solid fuel (auxiliary twisting agent) and providing a resource-saving coagulation treatment.
以上、本発明について、先ず本発明の粉末油凝固剤を説明し、次いで、この粉末油凝固剤を用いた流動可能型油凝固剤に関して説明する。 As described above, the powder oil coagulant of the present invention will be described first, and then the flowable type oil coagulant using this powder oil coagulant will be described.
本発明の粉末油凝固剤の説明前に、従来使用されている、例えば特許文献２に開示される粉末油凝固剤ａ、及び、その粉末油凝固剤ａの弱点の改善を図ることを目的に本発明者が以前に開発した粉末油凝固剤ｂについて以下に述べる。
特許文献２に開示される粉末油凝固剤ａは、ポリスチレンブロックとポリブダジエンブロックよりなるブロック共重合体で、この粉末油凝固剤は、下記表１に示すように合成油系潤滑油類に対しては、凝固能力が低かった。
Prior to the description of the powder oil coagulant of the present invention, for the purpose of improving the weak points of the powder oil coagulant a and the powder oil coagulant a conventionally used, for example, disclosed in Patent Document 2 The powder oil coagulant b previously developed by the present inventor will be described below.
The powder oil coagulant a disclosed in Patent Document 2 is a block copolymer composed of a polystyrene block and a polybudadiene block. This powder oil coagulant is used for synthetic oil-based lubricating oils as shown in Table 1 below. As a result, the coagulation ability was low.
そこで、本発明者は、この弱点を改善し、１種の粉末油凝固剤で多種の油類を凝固できる粉粒状ＳＥＥＰＳ（スチレン・エチレン・エチレン・プロピレン・スチレンブロック）と粉粒状ＳＥＢＳ（スチレン・エチレン・ブタジエン・スチレンブロック）からなる粉末油凝固剤ｂを開発した。
この粉末油凝固剤ｂの組成は、ＳＥＥＰＳを５５〜９５重量％、ＳＥＢＳを５〜４５重量％含むものである。その各種油分に対する凝固性能を表１に示すが、従来の粉末凝固剤ａにおいて、凝固能力の低かった油分に対する凝固能力を高めているが、さらに一層の改善が必要な状態であった。
Therefore, the present inventor has improved this weak point, and granular SEEPS (styrene / ethylene / ethylene / propylene / styrene block) and granular SEBS (styrene / styrene block) which can coagulate various oils with one kind of powder oil coagulant. We have developed a powder oil coagulant b consisting of ethylene, butadiene and styrene blocks.
The composition of this powder oil coagulant b contains 55 to 95% by weight of SEEPS and 5 to 45% by weight of SEBS. Table 1 shows the coagulation performance with respect to various oil components. In the conventional powder coagulant a, the coagulation capability with respect to the oil component with low coagulation capability was increased, but further improvement was necessary.
なお、表１の凝固能力の評価に際しては、常温下でビーカーに水を５０ｍｌと各種油を１０ｇ採り、各油凝固剤(試料)を２．５ｇ（油に対して２５重量％）添加し、１分間、スターラーにて撹拌して１５分間静置して凝固物を得た。その後、得られた凝固物を両手で軽く押し当て、油の滲み出しの状態を目視観察により評価した。 In the evaluation of the coagulation ability shown in Table 1, 50 ml of water and 10 g of various oils were taken into a beaker at room temperature, and 2.5 g (25% by weight based on oil) of each oil coagulant (sample) was added. The mixture was stirred for 1 minute with a stirrer and allowed to stand for 15 minutes to obtain a solidified product. Thereafter, the obtained solidified product was lightly pressed with both hands, and the state of oil oozing was evaluated by visual observation.
［本発明に係る粉末凝固剤］
表１に示される従来例２の粉末凝固剤ｂによって、１種類の粉末油凝固剤で多種の油類を凝固させる事が可能となったが、潤滑油系の油類に対しては、極僅かながら油の滲み出しが見られていた。
そこで、本発明者は、この２種類の成分からなる粉末油凝固剤ｂに対して、さらに検討を加えた結果、第３の構成要素として「粉粒状ＳＥＰ（スチレン・エチレン・プロピレンブロック共重合体）」を新たに加えることで、３種類のスチレンブロック共重合体が織りなす相乗効果を知見し、潤滑油系の油類に対しても、凝固状態の改良が実現でき、凝固物の油の滲み出しも殆ど無い粉末油凝固剤を得た。
表２に、本発明の粉末油凝固剤を構成する各成分の示す種々の油分に対する効果を示す。
[Powder coagulant according to the present invention]
The powder coagulant b of Conventional Example 2 shown in Table 1 makes it possible to coagulate various oils with one type of powder oil coagulant. There was a slight oozing of oil.
Therefore, as a result of further investigation on the powdered oil coagulant b composed of these two types of ingredients, the present inventor has found that a third component “powdered SEP (styrene / ethylene / propylene block copolymer)” ) ”Was added, and the synergistic effect of the three types of styrene block copolymers was weaved. It was possible to improve the coagulation state of lubricating oils, and the oil from the coagulated product A powdered oil coagulant with almost no discharge was obtained.
Table 2 shows the effects of various components constituting the powder oil coagulant of the present invention on various oils.
次に、ＳＥＥＰＳ、ＳＥＢＳ、ＳＥＰの３種類のスチレンブロック共重合体が占める割合が、その凝固能力を決めることから、組成の影響を調べ、以下に示す組成範囲を見出した。
［成分組成範囲］
・粉粒状ＳＥＥＰＳ ：４０〜９０重量％
・粉粒状ＳＥＢＳ ：５〜３０重量％
・粉粒状ＳＥＰ ：５〜３０重量％
を含む粉末油凝固剤である。
３種類の構成成分の割合が、この範囲おいては表２に示すように多種の油類に対して良好な凝固能力を示すが、この範囲外の組成では凝固に不具合を生じてしまう。
Next, since the proportion of the three kinds of styrene block copolymers of SEEPS, SEBS, and SEP determines the coagulation ability, the influence of the composition was examined, and the composition range shown below was found.
[Component composition range]
-Granular SEEPS: 40-90 wt%
・ Powdered SEBS: 5-30% by weight
・ Powdered SEP: 5 to 30% by weight
It is a powder oil coagulant containing.
The proportions of the three types of components show good coagulation ability for various oils as shown in Table 2 within this range, but if the composition is outside this range, problems occur in coagulation.
即ち、粉粒状ＳＥＥＰＳは、本発明に係る粉末油凝固剤の主成分といえるもので、「合成油系」に対する凝固能力が弱い特徴を持っている。その組成が４０重量％未満では、他の成分が多く含まれることになり、重油や鉱物油系に対する凝固作用が弱くなってしまう。逆に９０重量％を超えて含む場合には、他の成分の存在による効果が得られず潤滑油や合成油系に対する満足する凝固作用が得られなくなる。
一方、粉粒状ＳＥＢＳは、凝固能力において粉粒状ＳＥＥＰＳと同様の傾向を持っているが、潤滑油に対する凝固能力に劣っている。他方、粉粒状ＳＥＰは、他の成分が良好な凝固能力を示す「重油」や「鉱物油系」に対する凝固能力は劣るが、「潤滑油」や「合成油系のエンジンオイル」に対しては平均した凝固能力を有している。
That is, powdery SEEPS can be said to be the main component of the powder oil coagulant according to the present invention, and has a characteristic that the coagulation ability with respect to the “synthetic oil system” is weak. If the composition is less than 40% by weight, a large amount of other components are contained, and the coagulation action on heavy oil and mineral oil systems is weakened. On the other hand, when the content exceeds 90% by weight, the effect due to the presence of other components cannot be obtained, and a satisfactory coagulation action for a lubricating oil or synthetic oil system cannot be obtained.
On the other hand, granular SEBS has a tendency similar to that of granular SEEPS in coagulation ability, but is inferior in coagulation ability to lubricating oil. On the other hand, powdered SEP is inferior in coagulation ability to “heavy oil” and “mineral oil type” in which other components exhibit good coagulation ability, but for “lubricating oil” and “synthetic oil type engine oil” Has average clotting ability.
上記のような凝固能力を有する個々の構成成分の凝固剤における構成割合を適正化することによって、各種油分における凝固物からの油分漏れを生じ難い「ＳＥＥＰＳ／ＳＥＢＳ／ＳＥＰ」系粉末凝固剤が得られる。 By optimizing the composition ratios of the individual constituent components having the above solidification ability in the coagulant, it is possible to obtain a “SEEPS / SEBS / SEP” type powder coagulant that hardly causes oil leakage from the coagulum in various oils. It is done.
［本発明に係る流動可能型油凝固剤］
本発明に係る粉末油凝固剤を、ポンプ輸送テストを実施した結果、固体である本発明に係る粉末油凝固剤はポンプによる輸送は困難であった。
そこで、この粉末油凝固剤を用いたポンプによる輸送が可能な流動可能型油凝固剤を開発した。
開発に際しては、第一に海洋等への拡散投下の為には、ポンプ圧送可能である事、第二に長期保管が必須であるから、経時変化が起こらないこと、第三に海洋投下による環境に負荷を与えない点などを条件とした。
[Flowable oil coagulant according to the present invention]
As a result of conducting a pump transportation test on the powdered oil coagulant according to the present invention, it was difficult to transport the powdered oil coagulant according to the present invention, which was a solid, by a pump.
Therefore, we developed a flowable oil coagulant that can be transported by pump using this powdered oil coagulant.
During development, firstly, it is possible to pump by pump for the purpose of spreading and dropping into the ocean, and secondly, long-term storage is essential, so there is no change over time. The condition is that no load is applied to the.
本発明に係る流動可能型油凝固剤は、上記粉末油凝固剤に水溶性ゲル剤のみを調整剤に用いた油凝固剤で、その使用に際しては使用する油凝固剤の重量の７５〜２００重量％の水を加え、撹拌することによってポンプ圧送が容易に可能な流動性のある油凝固剤である。 The flowable type oil coagulant according to the present invention is an oil coagulant using only a water-soluble gel as a regulator in the powder oil coagulant, and the weight of the oil coagulant used is 75 to 200 wt. It is a fluid oil coagulant that can be easily pumped by adding% water and stirring.
本発明で使用する水溶性ゲル液は、上記第一から第三の条件を満たすものであれば特に限定されないが、具体的にはキサンタンガム及びフェノキシエタノールを含み水で希釈したものや、アクリル／アクリル酸アルキル（Ｃ１０−３０）コポリマーと、水酸化ナトリウム、及びフェノキシエタノールを水で希釈したものなどがある。
表３に、先に具体例として挙げた２種類の水溶性ゲル液を用いた本発明に係る流動可能型油凝固剤の凝固能力を示すが、ポンプ圧送の可能の有無だけであれば、両者共に凝固性能に大差は無い。しかし、僅かながらでも後者は、拡散投下によって、油類への乳化による環境汚染も懸念される事から、その選択には、環境汚染に対する注意を要する。
The water-soluble gel solution used in the present invention is not particularly limited as long as it satisfies the first to third conditions. Specifically, xanthan gum and phenoxyethanol diluted with water or acrylic / acrylic acid Examples include alkyl (C10-30) copolymer, sodium hydroxide, and phenoxyethanol diluted with water.
Table 3 shows the coagulation ability of the flowable oil coagulant according to the present invention using the two types of water-soluble gel liquids mentioned above as specific examples. There is no big difference in coagulation performance. However, since the latter may cause environmental contamination due to emulsification in oils due to diffusion, the selection requires attention to environmental contamination.
粉末油凝固剤と水溶性ゲル液の混練物が油類と接触することによって、吸着凝固できる点、及び水を加え撹拌することで、海洋等への拡散投下の為にポンプ圧送ができる点の２点を満足する為に、水溶性ゲル液の添加量は、粉末油凝固剤の全体量に対し、１５〜８５重量％が望ましい。 A mixture of powdered oil coagulant and water-soluble gel solution comes into contact with oils, so that it can be adsorbed and solidified. In order to satisfy the two points, the amount of the water-soluble gel solution added is preferably 15 to 85% by weight with respect to the total amount of the powder oil coagulant.
流動可能型油凝固剤の使用に際しては、圧送ポンプを使用して輸送を行う場合、先ず流動可能型油凝固剤の重量に対し、０．７５〜２倍の水を加え、撹拌により流動性が調製可能な流動型油凝固剤を作製する。万一、調整後に保存が長期に亘り、この流動型油凝固剤が放湿し、含水量が少なくなった場合でも、適度に水を加え撹拌することによって、その流動性や凝固性能が回復できる。 When using a flowable type oil coagulant, when transporting using a pressure pump, first, 0.75 to 2 times the water is added to the weight of the flowable type oil coagulant, and the flowability is increased by stirring. A fluid oil coagulant that can be prepared is prepared. Even if the fluidized oil coagulant is dehumidified for a long period of time after adjustment and the water content decreases, the fluidity and coagulation performance can be recovered by adding water and stirring appropriately. .
また、圧送ポンプを用いて圧送、拡散投下において、流動型油凝固剤の拡散放出には、放出口先端のノズル径は、直径が８ｍｍ〜１５ｍｍ程度が望ましい。さらに、油凝固物を簡単に回収する為に、吸引ポンプ等を使用し、回収量の規模や作業環境で、作業条件に応じて、水抜けフレコン、メッシュスクリーン、口布、水抜け袋等々、適宜選定する事ができる。 In addition, when the fluid-type oil coagulant is diffused and released using a pressure-feed pump, the nozzle diameter at the tip of the discharge port is preferably about 8 mm to 15 mm. Furthermore, in order to easily collect the oil coagulum, a suction pump or the like is used, and depending on the working conditions, in the scale of the amount to be collected and the working environment, water draining flexible container, mesh screen, mouth cloth, water draining bag, etc., You can select as appropriate.
以下に、実施例を用いて本発明をさらに説明する。
ＳＥＥＰＳ、ＳＥＢＳ、ＳＥＰが、表４に示すようになるように各試料を秤量、混合して実施例に係る粉末凝固剤を作製した。
その作製した粉末凝固剤を用いて、表４に示す４種類の「凝固対象油類」について、下記条件で凝固試験を行い、評価した。
The present invention will be further described below with reference to examples.
Each sample was weighed and mixed so that SEEPS, SEBS, and SEP were as shown in Table 4 to prepare a powder coagulant according to the example.
Using the produced powder coagulant, a solidification test was performed on the four types of “oils to be solidified” shown in Table 4 under the following conditions and evaluated.
［試験条件］
常温下でビーカーに水を５０ｍｌと各種油を１０ｇ採り、各油凝固剤(試料)を２．５ｇ（油に対して２５重量％）添加し、１分間、スターラーにて撹拌して１５分間静置して凝固物を得た。その後、得られた凝固物を両手で軽く押し当て、油の滲み出しの状態を目視観察して評価した。
[Test conditions]
At room temperature, take 50 ml of water and 10 g of various oils in a beaker, add 2.5 g of each oil coagulant (sample) (25% by weight to the oil), stir with a stirrer for 1 minute, and leave for 15 minutes. To obtain a coagulum. Thereafter, the obtained solidified product was lightly pressed with both hands, and the state of oil oozing was visually observed and evaluated.
ＳＥＥＰＳを６０重量％、ＳＥＢＳを２０重量％、ＳＥＰを２０重量％の割合になるように各試料を秤量、混合、攪拌して実施例１に係る粉末油凝固剤を作製、凝固試験を行い評価した。
その結果を表４に示す。
Each sample was weighed, mixed, and stirred so that the ratio of SEEPS was 60% by weight, SEBS was 20% by weight, and SEP was 20% by weight. did.
The results are shown in Table 4.
（比較例１）
ＳＥＥＰＳを２０重量％、ＳＥＢＳを６０重量％、ＳＥＰを２０重量％の割合になるように各試料を秤量、混合して比較例１に係る粉末油凝固剤を作製、凝固試験を行い評価した。
その結果を表４に示す。
(Comparative Example 1)
Each sample was weighed and mixed so that SEEPS was 20% by weight, SEBS was 60% by weight, and SEP was 20% by weight to prepare a powdered oil coagulant according to Comparative Example 1, and a solidification test was conducted and evaluated.
The results are shown in Table 4.
（比較例２）
ＳＥＥＰＳを２０重量％、ＳＥＢＳを２０重量％、ＳＥＰを６０重量％の割合になるように各試料を秤量、混合して比較例２に係る粉末油凝固剤を作製、凝固試験を行い評価した。
その結果を表４に示す。
(Comparative Example 2)
Each sample was weighed and mixed so that SEEPS was 20% by weight, SEBS was 20% by weight, and SEP was 60% by weight to prepare a powder oil coagulant according to Comparative Example 2, and a solidification test was conducted and evaluated.
The results are shown in Table 4.
表４に見られるように、本発明に係る粉末油凝固剤である実施例１では、試験した４種類の油類において、満足すべき凝固能力を示していることがわかり、これまでの従来例２の粉末凝固剤より大きく優れている。
ＳＥＢＳが多い比較例１では「潤滑油」や「合成油系」に対する凝固能力の向上が見られなかった。また、ＳＥＰが多く、他の２成分が少ない比較例２は、「重油」、「鉱物油系」に対する凝固能力が大きく低下してしまっていた。
As can be seen in Table 4, in Example 1 which is a powder oil coagulant according to the present invention, it was found that the four types of oils tested showed satisfactory coagulation ability, and the conventional examples so far Greater than 2 powder coagulants.
In Comparative Example 1 with a large amount of SEBS, no improvement in coagulation ability with respect to “lubricating oil” or “synthetic oil system” was observed. Further, in Comparative Example 2 having a large amount of SEP and a small amount of the other two components, the coagulation ability with respect to “heavy oil” and “mineral oil system” was greatly reduced.
以下、流動可能型油凝固剤の実施例を示す。 Examples of flowable oil coagulants are shown below.
実施例１の粉末油凝固剤を用い、調製剤として、その粉末凝固剤の重量に対して、６５重量％の水溶性ゲル剤（表３試料１記載のキサンタンガム１重量％及びフェノキシエタノール１重量％を水で希釈して１００重量％としたもの）のみを添加、攪拌して、実施例２に係る流動可能型油凝固剤を作製した。
その作製した流動可能型油凝固剤の１２５重量％の量の水を加えて攪拌して流動型油凝固剤を作製、攪拌後静置した状態での分離時間測定、及びポンプ圧送試験を行った。
その結果を表５に示す。
Using the powdered oil coagulant of Example 1 as a preparation, 65% by weight of a water-soluble gel (1% by weight of xanthan gum and 1% by weight of phenoxyethanol described in Table 1 Sample 1) is based on the weight of the powder coagulant. Only 100% by weight diluted with water) was added and stirred to prepare a flowable oil coagulant according to Example 2.
A fluid type oil coagulant was prepared by adding water of 125% by weight of the produced flowable type oil coagulant and agitated, and the separation time measurement and the pumping test were carried out in a state of standing after agitation. .
The results are shown in Table 5.
（比較例３）
調製剤として、粉末油凝固剤に対し、１００重量％の水溶性ゲル剤と界面活性剤を３重量％の２種類を添加して作製した以外は、実施例２と同様の条件で試験用の流動型油凝固剤を作製、実施例２と同様の試験を行った。
その結果を表５に示す。
(Comparative Example 3)
For the test under the same conditions as in Example 2 except that the preparation was made by adding two types of 100% by weight of a water-soluble gel and a surfactant to 3% by weight of the powder oil coagulant. A fluid type oil coagulant was prepared and tested in the same manner as in Example 2.
The results are shown in Table 5.
（従来例３）
従来例２の粉末油凝固剤を用い、その粉末油凝固剤の重量に対して、１６０重量％の水溶性ゲル剤と６０重量％の濃度５％デンプン溶液と２．５重量％の界面活性剤の３種類の材料を加え、攪拌混合して従来例３に係る流動可能型油凝固剤を作製した。
その作製した流動可能型油凝固剤の２００重量％の量の水を加えて攪拌して流動型油凝固剤を作製、実施例２と同様の試験を行った。
その結果を表５に示す。
(Conventional example 3)
Using the powdered oil coagulant of Conventional Example 2, 160% by weight of water-soluble gel, 60% by weight of 5% starch solution and 2.5% by weight of surfactant based on the weight of the powdered oil coagulant The flowable type oil coagulant according to Conventional Example 3 was prepared by adding the above three types of materials and stirring and mixing.
A flow type oil coagulant was prepared by adding 200% by weight of water of the produced flowable type oil coagulant and stirring, and the same test as in Example 2 was performed.
The results are shown in Table 5.
表５から、各供試材共に流動型油凝固剤であることから、そのポンプ圧送状態（輸送性）は良好であったが、本発明に係る実施例２では、攪拌停止から凝固剤成分が分離開始する時間が比較例３及び従来例３より極めて短く、油面に投下された流動型油凝固剤は、その油面上で直ちに作用し、油分に対する凝固効果を容易に発揮できる。 From Table 5, since each test material is a fluid type oil coagulant, its pumping condition (transportability) was good, but in Example 2 according to the present invention, the coagulant component was stopped from the stop of stirring. The time for starting the separation is much shorter than Comparative Example 3 and Conventional Example 3, and the fluidized oil coagulant dropped on the oil surface acts immediately on the oil surface and can easily exhibit the coagulation effect on the oil.
Claims (4)
粉粒状のスチレン・エチレン・ブチレン・スチレンブロック共重合体と、
粉粒状のスチレン・エチレン・プロピレン・ブロック共重合体とからなることを特徴とする粉末油凝固剤。 Powdery styrene / ethylene / ethylene / propylene / styrene block copolymer;
Powdered styrene / ethylene / butylene / styrene block copolymer,
A powder oil coagulant characterized by comprising a powdery styrene / ethylene / propylene / block copolymer.
粉粒状のスチレン・エチレン・ブチレン・スチレンブロック共重合体を５〜３０重量％、
粉粒状のスチレン・エチレン・プロピレン・ブロック共重合体を５〜３０重量％からなることを特徴とする粉末油凝固剤。 40 to 90% by weight of powdery styrene / ethylene / ethylene / propylene / styrene block copolymer,
5-30% by weight of powdery styrene / ethylene / butylene / styrene block copolymer,
A powder oil coagulant comprising 5 to 30% by weight of a powdery styrene / ethylene / propylene / block copolymer.
粉粒状のスチレン・エチレン・ブチレン・スチレンブロック共重合体と、
粉粒状のスチレン・エチレン・プロピレン・ブロック共重合体とからなる粉末油凝固剤、
又は、粉粒状のスチレン・エチレン・エチレン・プロピレン・スチレンブロック共重合体を４０〜９０重量％、
粉粒状のスチレン・エチレン・ブチレン・スチレンブロック共重合体を５〜３０重量％、
粉粒状のスチレン・エチレン・プロピレン・ブロック共重合体を５〜３０重量％からなる粉末油凝固剤と、
水溶性ゲル液のみとからなるゲル体である流動可能型油凝固剤と希釈水からなるゾル状態の流動型油凝固剤であって、
前記希釈水の重量が、前記流動可能型油凝固剤の重量に対し、０．７５〜２倍の重量であり、
前記ゾル状態の流動型油凝固剤の流動性が、前記希釈水により調製されていることを特徴とする流動型油凝固剤。 Powdery styrene / ethylene / ethylene / propylene / styrene block copolymer;
Powdered styrene / ethylene / butylene / styrene block copolymer,
A powder oil coagulant comprising a powdery styrene / ethylene / propylene / block copolymer,
Alternatively, 40 to 90% by weight of powdery styrene / ethylene / ethylene / propylene / styrene block copolymer,
5-30% by weight of powdery styrene / ethylene / butylene / styrene block copolymer,
A powder oil coagulant comprising 5 to 30% by weight of a granular styrene / ethylene / propylene / block copolymer;
A fluid type oil coagulant in a sol state consisting of a flowable type oil coagulant which is a gel body consisting only of a water-soluble gel liquid and a dilution water,
The weight of the dilution water is 0.75 to 2 times the weight of the flowable oil coagulant,
A fluid oil coagulant characterized in that the fluidity of the fluid oil coagulant in the sol state is prepared by the dilution water.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5219190A (en) * | 1975-08-06 | 1977-02-14 | Asahi Chem Ind Co Ltd | Oil treating material |
| JPS5231992A (en) * | 1975-08-25 | 1977-03-10 | Asahi Chem Ind Co Ltd | Oil-treating material by adsorption and absorption |
| JPH07102238A (en) * | 1993-10-06 | 1995-04-18 | Alpha Japan:Kk | Oil-solidifying agent |
| JPH07506614A (en) * | 1992-05-13 | 1995-07-20 | レイケム・リミテッド | gel |
| JPH09137185A (en) * | 1995-11-14 | 1997-05-27 | Alpha Japan:Kk | Oil-solidifying agent |
| JPH09137184A (en) * | 1995-11-10 | 1997-05-27 | Ii C Ii:Kk | Oil coagulant |
| JPH10147773A (en) * | 1996-11-20 | 1998-06-02 | Ii C Ii:Kk | Oil coagulant |
| JPH10176162A (en) * | 1996-12-20 | 1998-06-30 | Ii C Ii:Kk | Lubricant-solidifying agent |
| JP2006206699A (en) * | 2005-01-27 | 2006-08-10 | Kansai Electric Power Co Inc:The | Flowable gel-like oil-coagulating agent and method and apparatus for filling the same |
-
2015
- 2015-10-13 JP JP2015202298A patent/JP6055061B1/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5219190A (en) * | 1975-08-06 | 1977-02-14 | Asahi Chem Ind Co Ltd | Oil treating material |
| JPS5231992A (en) * | 1975-08-25 | 1977-03-10 | Asahi Chem Ind Co Ltd | Oil-treating material by adsorption and absorption |
| JPH07506614A (en) * | 1992-05-13 | 1995-07-20 | レイケム・リミテッド | gel |
| JPH07102238A (en) * | 1993-10-06 | 1995-04-18 | Alpha Japan:Kk | Oil-solidifying agent |
| JPH09137184A (en) * | 1995-11-10 | 1997-05-27 | Ii C Ii:Kk | Oil coagulant |
| JPH09137185A (en) * | 1995-11-14 | 1997-05-27 | Alpha Japan:Kk | Oil-solidifying agent |
| JPH10147773A (en) * | 1996-11-20 | 1998-06-02 | Ii C Ii:Kk | Oil coagulant |
| JPH10176162A (en) * | 1996-12-20 | 1998-06-30 | Ii C Ii:Kk | Lubricant-solidifying agent |
| JP2006206699A (en) * | 2005-01-27 | 2006-08-10 | Kansai Electric Power Co Inc:The | Flowable gel-like oil-coagulating agent and method and apparatus for filling the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2017075215A (en) | 2017-04-20 |
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