WO2016151777A1 - Oil-water separation method for oil-containing scum and oil-water separation agent for oil-containing scum - Google Patents

Oil-water separation method for oil-containing scum and oil-water separation agent for oil-containing scum Download PDF

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Publication number
WO2016151777A1
WO2016151777A1 PCT/JP2015/058989 JP2015058989W WO2016151777A1 WO 2016151777 A1 WO2016151777 A1 WO 2016151777A1 JP 2015058989 W JP2015058989 W JP 2015058989W WO 2016151777 A1 WO2016151777 A1 WO 2016151777A1
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Prior art keywords
oil
scum
alkyl ether
polyoxyalkylene alkyl
viscosity
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PCT/JP2015/058989
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French (fr)
Japanese (ja)
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たかし 吉川
駿輔 村上
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栗田工業株式会社
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Priority to PCT/JP2015/058989 priority Critical patent/WO2016151777A1/en
Publication of WO2016151777A1 publication Critical patent/WO2016151777A1/en

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning

Definitions

  • the present invention relates to an oil-water separation method for oil-containing scum and an oil-water separation agent for oil-containing scum.
  • oil-containing wastewater In the rolling process of metals such as cold rolling, oil for lubrication and water for cooling are necessary, and oil-containing wastewater is generated.
  • the oil-containing wastewater generated by the metal rolling process or the like is separated into water and oil in the oil-water separation tank.
  • the separated water is collected and reused by cold rolling or sent to a wastewater treatment facility.
  • the oil floats as scum during oil-water separation.
  • Scum containing oil (hereinafter referred to as “oil-containing scum”) has a calorific value, but contains about 40 to 70% of water, and is difficult to reuse as fuel. For this reason, oil-impregnated scum is often incinerated as industrial waste.
  • Patent Documents 1 to 3 In order to reuse oil-containing scum as fuel, it is necessary to reduce the moisture in the oil-containing scum. As oil-water separation treatment of oil-containing wastewater or oil-containing scum, the techniques of Patent Documents 1 to 3 have been proposed.
  • Patent Document 1 a mineral acid such as hydrochloric acid is added to an oil having a high water content such as emulsion oil generated after the degreasing process of the metal surface treatment process, and the oil is separated by stirring and standing.
  • a method of reusing as fuel is disclosed.
  • the oil phase and clarification can be obtained by adding a nonionic surfactant having an HLB value lower than that of the surfactant to the oil-containing wastewater containing the nonionic surfactant without heating the wastewater.
  • a method for separating the aqueous phase is disclosed.
  • Patent Document 3 after floating oil is separated from oil-containing wastewater in an oil separation tank, the floating oil is further separated in a pressure floating tank without chemical injection, and the floating oil is removed in two stages.
  • a method is disclosed in which a flocculant is added, the separated oil is floated as scum in a flocculation pressurized flotation concentration tank, and the floated scum is incinerated.
  • JP 58-84491 A Japanese Patent No. 4625894 Japanese Patent Publication No. 4-10397
  • Patent Document 1 has a problem that it is necessary to make the treatment equipment acid-resistant because of the addition of acid, and that the treatment using the existing equipment is difficult.
  • the technique of Patent Document 2 has a problem that it is difficult to cope with the case where the type of emulsifier contained in the oil-containing wastewater cannot be specified.
  • the method of Patent Document 2 considers only oil-water separation of oil-containing wastewater, and does not consider oil-water separation of oil-containing scum, which has a higher viscosity than oil-containing wastewater and has different properties from oil-containing wastewater.
  • the technique of Patent Document 3 requires three stages of processing and has the problem that it is necessary to add equipment.
  • patent document 3 does not consider the advanced oil-water separation which reuses oil-containing scum as a fuel. Furthermore, since there are various types of oils and additives used in cold rolling, oil-containing scum generated by cold rolling does not have stable oil properties. Depending on the difference in the properties of the oil, there are cases where the oil / water separation can be performed when the oil / water separating agent is added, and there are cases where the oil / water separation cannot be performed, but Patent Documents 1 to 3 do not consider the difference in the properties of the oil at all.
  • the present invention has been made under such circumstances, and an object thereof is to provide an oil-water separation method for oil-containing scum capable of oil-water separation regardless of the properties of the oil-containing scum. Moreover, an object of this invention is to provide the oil-water separation agent used for the said method.
  • An oil impregnation step comprising selecting a polyoxyalkylene alkyl ether according to the following criteria (a) to (c) according to the viscosity of the oil impregnation scum and adding the selected polyoxyalkylene alkyl ether to the oil impregnation scum.
  • Scum oil-water separation method comprising selecting a polyoxyalkylene alkyl ether according to the following criteria (a) to (c) according to the viscosity of the oil impregnation scum and adding the selected polyoxyalkylene alkyl ether to the oil impregnation scum.
  • Scum oil-water separation method comprising selecting a polyoxyalkylene alkyl ether according to the following criteria (a) to (c) according to the viscosity of the oil impregnation scum and adding the selected polyoxyalkylene alkyl ether to the oil impregnation scum.
  • Scum oil-water separation method comprising selecting a poly
  • An oil-water separator for oil-impregnated scum generated in a rolling process comprising a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 and an alkyl group derived from a secondary alcohol.
  • the oil-impregnated scum can be separated from water regardless of the nature of the oil-impregnated scum, and the oil-impregnated scum can be reused as fuel.
  • the oil-water separation method A of the oil-impregnated scum of the present invention selects a polyoxyalkylene alkyl ether according to the following criteria (a) to (c) according to the viscosity of the oil-impregnated scum, and oils the selected polyoxyalkylene alkyl ether: It includes a step of adding to the scum.
  • the oil-impregnated scum as used in the present invention includes at least the oil component (floating oil) separated in the oil-water separation tank, and, depending on the case, components other than oil components such as moisture taken out simultaneously with the oil component during oil-water separation, and It contains components added after oil-water separation, such as water sprayed on the oil-containing scum.
  • the oil-impregnated scum applicable to the oil-water separation method of the oil-impregnated scum of the present invention is not particularly limited.
  • an oil-impregnated drainage generated by a metal rolling process such as cold rolling or the like can be mentioned.
  • the oil content in the oil-containing scum is not particularly limited, but is usually 30 to 60% by mass.
  • oil-impregnated scum generated from oil-containing wastewater such as cold rolling and other metal rolling processes does not have stable oil properties.
  • the properties of the oil are not stable, the viscosity of the oil-containing scum is not stable.
  • the present inventors have found that the viscosity of oil-containing scum has a great influence on the results of oil-water separation, and selected oil-water separation agents based on the following criteria (a) to (c) according to the viscosity of oil-containing scum By doing so, it was found that the oil-containing scum can be separated into water regardless of the viscosity of the oil-containing scum, and the oil-containing scum can be reused as fuel.
  • Oil-impregnated scum has a viscosity at 20 ° C. of less than 1000 mPa ⁇ s
  • a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 is added.
  • Oil-impregnated scum often takes the form of water-in-oil (W / O) emulsions, with an HLB value of about 3-7.
  • the oil-impregnated scum having a viscosity at 20 ° C. of less than 1000 mPa ⁇ s is a state in which water droplets are relatively mobile in a water-in-oil (W / O) emulsion.
  • polyoxyalkylene alkyl ether a having an HLB value of 10 to 13.5
  • W water droplets in oil
  • Oil-water separation of oil-impregnated scum using polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 is more effective when the viscosity of oil-impregnated scum at 20 ° C is 500 mPa ⁇ s or more, and when it is 800 mPa ⁇ s or more It is even more effective.
  • the polyoxyalkylene alkyl ether a is not particularly limited as long as it has an HLB value of 10 to 13.5.
  • the polyoxyalkylene alkyl ether a can be obtained, for example, by addition polymerization of an alkylene oxide such as ethylene oxide and propylene oxide to an alcohol, and examples thereof include those represented by the following formulas (1) and (2).
  • R 1 —O— (R 2 —O) m1 —H (1)
  • R 1 represents a linear or branched alkyl group having 8 to 22 carbon atoms
  • R 2 represents an alkylene group having 2 or 3 carbon atoms
  • m1 represents an integer of 2 to 20.
  • R 3 O— (R 4 —O) m2 — (R 5 —O) m3 —H (2)
  • R 3 represents a linear or branched alkyl group having 8 to 22 carbon atoms
  • R 4 represents a linear or branched alkylene group having 2 to 20 carbon atoms
  • R 5 represents a carbon number of 1 to 10 R 4 and R 5 are different from each other
  • m2 and m3 each represent an integer of 0 to 10, but m2 and m3 are not 0 at the same time.
  • the carbon number of R 1 in the formula (1) and R 3 in the formula (2) is preferably 10 to 14, more preferably 12 carbon atoms.
  • the number of carbon atoms of R 2 in the formula (1) is preferably 2.
  • polyoxyalkylene alkyl ether b When a polyoxyalkylene alkyl ether having an alkyl group derived from a secondary alcohol (hereinafter sometimes referred to as “polyoxyalkylene alkyl ether b”) is added to such an oil-containing scum, water droplets in oil ( It is considered that the components of the (W / O) type emulsion are separated into water and oil, and the oil / water separation effect can be promoted.
  • Oil-water separation of oil-containing scum using a polyoxyalkylene alkyl ether whose alkyl group is derived from a secondary alcohol is more effective when the oil-containing scum has a viscosity at 20 ° C. of 3000 to 10,000 mPa ⁇ s, and 5500 to 7000 mPa ⁇ s. It is more effective in the case of s.
  • the polyoxyalkylene alkyl ether b is not particularly limited as long as the alkyl group is derived from a secondary alcohol.
  • the polyoxyalkylene alkyl ether b can be obtained, for example, by addition polymerization of an alkylene oxide such as ethylene oxide and propylene oxide to a secondary alcohol, and examples thereof include those represented by the following formulas (3) and (4). It is done.
  • R 6 represents a branched alkyl group having 8 to 22 carbon atoms
  • R 7 represents an alkylene group having 2 or 3 carbon atoms
  • m4 represents an integer of 2 to 20.
  • R 8 represents a branched alkyl group having 8 to 22 carbon atoms
  • R 9 is a linear or branched alkylene group having 2 to 20 carbon atoms
  • R 10 is a linear chain having 1 to 10 carbon atoms.
  • R 9 and R 10 are different from each other, and m5 and m6 each represent an integer of 0 to 10, but m5 and m6 are not 0 at the same time.
  • those represented by the formula (3) are preferable.
  • the carbon number of R 6 in the formula (3) and R 8 in the formula (4) is preferably 10 to 14, more preferably 12 carbon atoms.
  • the number of carbon atoms of R 7 in the formula (3) is preferably 2.
  • oil-containing scum has a viscosity at 20 ° C. of 1000 mPa ⁇ s or more and less than 2000 mPa ⁇ s
  • a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 and / or an alkyl group derived from a secondary alcohol Add ether.
  • the oil-impregnated scum having a viscosity at 20 ° C. of 1000 mPa ⁇ s or more and less than 2000 mPa ⁇ s means that the oil content in the oil-containing scum is intermediate between the oil content of the scum of the reference (a) and the oil content of the scum of the reference (c).
  • both the polyoxyalkylene alkyl ether a and / or the polyoxyalkylene alkyl ether b can exhibit the oil-water separation effect.
  • the polyoxyalkylene alkyl ether of the standard (b) the polyoxyalkylene alkyl ether exemplified in the standard (a) and / or the polyoxyalkylene alkyl ether exemplified in the standard (b) can be used.
  • the HLB value is 10 to 10 when the oil-impregnated scum has a viscosity at 20 ° C. of 1000 mPa ⁇ s to 1500 mPa ⁇ s. It is preferable to add 13.5 polyoxyalkylene alkyl ether, and when the oil-containing scum has a viscosity at 20 ° C.
  • polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 It is also preferable to add polyoxyalkylene alkyl ethers whose alkyl groups are derived from secondary alcohols.
  • the method for calculating the viscosity of oil-impregnated scum at 20 ° C. is as follows: (1) Method of measuring the viscosity of oil-impregnated scum adjusted to 20 ° C., (2) Other temperature (for example, temperature at the time of collecting oil-impregnated scum, 30 minutes at room temperature The temperature of the oil-impregnated scum that has been left standing, etc.), and calculating the viscosity of the oil-impregnated scum from a straight line obtained by plotting the logarithm of ln ⁇ -1 / T. (3) When the composition of the oil-impregnated scum is known May be calculated by a viscosity calculation formula such as Andre's formula.
  • Oil-containing scum oil-water separation method B In the oil-water separation method B of the oil-containing scum of the present invention, a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 and an alkyl group derived from a secondary alcohol is added to the oil-containing scum.
  • the polyoxyalkylene alkyl ether a is effective for oil-water separation, and the viscosity of the oil-containing scum of 20 ° C. Is 1000 mPa ⁇ s or more and less than 2000 mPa ⁇ s, polyoxyalkylene alkyl ether a and / or polyoxyalkylene alkyl ether b is effective for oil-water separation, and the viscosity of oil-containing scum at 20 ° C. is 2000 mPa ⁇ s or more.
  • the polyoxyalkylene alkyl ether b is effective for oil-water separation. Accordingly, a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 and an alkyl group derived from a secondary alcohol (hereinafter sometimes referred to as “polyoxyalkylene alkyl ether c”) is a polyoxyalkylene alkyl ether. It has both the properties of oxyalkylene alkyl ether a and polyoxyalkylene alkyl ether b, and can exhibit an oil-water separation effect regardless of the viscosity of the oil-containing scum.
  • the polyoxyalkylene alkyl ether c can be obtained, for example, by addition polymerization of a secondary alcohol with an alkylene oxide such as ethylene oxide or propylene oxide, and those represented by the following formulas (5) and (6) are mentioned. It is done.
  • R 11 represents a branched alkyl group having 8 to 22 carbon atoms
  • R 12 represents an alkylene group having 2 or 3 carbon atoms
  • m7 represents an integer of 2 to 20.
  • R 13 represents a branched alkyl group having 8 to 22 carbon atoms
  • R 14 is a linear or branched alkylene group having 2 to 20 carbon atoms
  • R 15 is a straight chain having 1 to 10 carbon atoms.
  • R 14 and R 15 are different from each other, and m8 and m9 each represent an integer of 0 to 10, but m8 and m9 are not 0 simultaneously.
  • those represented by the formula (5) are preferable.
  • the carbon number of R 11 in formula (5) and R 13 in formula (6) is preferably 10 to 14, and more preferably 12 carbon atoms.
  • the number of carbon atoms of R 12 in the formula (5) is preferably 2.
  • the viscosity of the oil-impregnated scum in the oil-water separation method B of the oil-impregnated scum is not particularly limited, but is more effective when the oil-impregnated scum has a viscosity at 20 ° C. of 500 to 10,000 mPa ⁇ s, and more effective when the viscosity is 800 to 7000 mPa ⁇ s. It is.
  • the polyoxyalkylene alkyl ether is preferably added in an amount of 5 to 20 g / L, more preferably 10 to 15 g / L, based on the oil-containing scum.
  • the total amount of polyoxyalkylene alkyl ethers may be set within the above range.
  • the form of adding the polyoxyalkylene alkyl ether may be added as it is, or may be added after being diluted with a solvent such as a solvent or water.
  • concentration of the polyoxyalkylene alkyl ether in the diluted solution is preferably 10 to 95% by mass.
  • the temperature and pH of the oil-containing scum when adding the polyoxyalkylene alkyl ether are not particularly limited.
  • the temperature is preferably 5 to 70 ° C, more preferably 25 to 35 ° C, and particularly preferably 30 ° C.
  • the pH is preferably 5 to 9, more preferably 6 to 7, and particularly preferably 6.5.
  • additive components such as an anionic surfactant and a cationic surfactant can be added without departing from the object of the present invention.
  • additive components can be used alone or in combination of two or more.
  • the oil / water separator A for oil-impregnated scum of the present invention comprises a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5, and the oil-impregnated scum having a viscosity at 20 ° C. of less than 2000 mPa ⁇ s generated in the rolling process. It is an oil-water separator for use. That is, the oil / water separator A contains the polyoxyalkylene alkyl ether a described above.
  • the oil / water separating agent A may contain components other than the polyoxyalkylene alkyl ether a, but the polyoxyalkylene alkyl ether a in the total solid content of the oil / water separating agent A may be 80% by mass or more. Preferably, the content is 90% by mass or more, and more preferably 100% by mass.
  • the oil / water separator A is more effective when the viscosity of the oil-containing scum at 20 ° C. is 500 mPa ⁇ s or more and 1500 mPa ⁇ s or less, and more effective when the viscosity is 800 mPa ⁇ s or more and 1500 mPa ⁇ s or less.
  • Oil / water separator B for oil-impregnated scum comprises a polyoxyalkylene alkyl ether having an alkyl group derived from a secondary alcohol, and has an oil-impregnating viscosity at 20 ° C. of 1000 mPa ⁇ s or more generated in a rolling process.
  • Oil / water separator for scum That is, the oil / water separator B contains the polyoxyalkylene alkyl ether b described above.
  • the oil / water separating agent B may contain components other than the polyoxyalkylene alkyl ether b, but the polyoxyalkylene alkyl ether b in the total solid content of the oil / water separating agent B is 80% by mass or more. Preferably, the content is 90% by mass or more, and more preferably 100% by mass.
  • the oil / water separating agent B is more effective when the viscosity of the oil-containing scum at 20 ° C. is 1300 mPa ⁇ s or more and 10,000 mPa ⁇ s or less, and more effective when the viscosity is 1500 mPa ⁇ s or more and 80000 mPa ⁇ s, and 5500 mPa ⁇ s or more. Even more effective in the case of 7000 mPa ⁇ s or less.
  • Oil / water separator C for oil-containing scum The oil / water separating agent C for oil-impregnated scum of the present invention is generated in a rolling process, having an HLB value of 10 to 13.5 and containing a polyoxyalkylene alkyl ether having an alkyl group derived from a secondary alcohol. It is an oil-water separator for oil-impregnated scum. That is, the oil / water separator C contains the polyoxyalkylene alkyl ether c described above.
  • the oil / water separating agent C may contain components other than the polyoxyalkylene alkyl ether c, but the polyoxyalkylene alkyl ether c in the total solid content of the oil / water separating agent C may be 80% by mass or more. Preferably, the content is 90% by mass or more, and more preferably 100% by mass.
  • the oil / water separator C is more effective when the viscosity of the oil-containing scum at 20 ° C. is 500 to 10,000 mPa ⁇ s, and more effective when the viscosity is 800 to 7000 mPa ⁇ s.
  • Viscosity measurement of oil-impregnated scum Four types of oil-impregnated scum (oil-impregnated scum 1 to 4) collected in an oil-water separation tank of oil-impregnated wastewater that has undergone cold rolling are used in a thermostat set at 20 ° C, using a B-type viscometer, Rotor No. The measurement was performed at 6, 40 rpm. The results are shown below.
  • Scum 1 Viscosity 950 mPa ⁇ s
  • Scum 2 Viscosity 1400 mPa ⁇ s
  • Scum 3 Viscosity 6600 mPa ⁇ s
  • Scum 4 Viscosity 6000 mPa ⁇ s
  • the sample in the test tube was stirred with a spatula for 120 seconds to mix the oil-containing scum and the drug. After standing in a thermostatic bath at 30 ° C. for one day, the amount of water separated from the height of the aqueous phase was measured, and the water concentration remaining in the oil-containing scum was calculated.
  • the oil-impregnated scum and the chemical were used in the combinations shown in Tables 1 and 2. 2-3. Calculation of moisture reduction rate of oil-impregnated scum by oil-water separation treatment The water concentration in the oil-impregnated scum before oil-water separation is “X%”, and the water concentration of the oil-impregnated scum after oil-water separation is “Y%”.
  • the moisture reduction rate of the oil-impregnated scum was calculated.
  • a sample having a moisture reduction rate of 50% or more was designated “A”
  • B a sample having a moisture reduction rate of 30% or more and less than 50%
  • C a sample having a moisture reduction rate of less than 30%
  • Drugs used 1 Nonionic surfactant (polyoxyethylene lauryl ether; manufactured by Sanyo Chemical Industries, Emalmin NL-70; HLB value 12.4)
  • Agent 2 Nonionic surfactant (polyoxyalkylene alkyl ether; manufactured by Sanyo Chemical Industries, NAROACTY CL-85; HLB value 12.6)
  • Agent 3 Nonionic surfactant (mixture of polyoxyethylene oleyl ether and polyoxyethylene cetyl ether; manufactured by Sanyo Chemical Industries, Emalmin 110; HLB value 13.2)
  • Agent 4 Nonionic surfactant (polyoxyethylene alkyl ether; manufactured by Sanyo Chemical Industries, Cedran SF-506; HLB value 6.1)
  • Agent 5 Nonionic surfactant (polyoxyethylene alkyl ether; Sanyo Chemical Industries, Sannonic SS-50; HLB value 10.5)
  • Agent 6 Nonionic surfactant (polyoxyethylene alkyl ether; Sanyo Chemical Industries, Sannonic SS-90;
  • the polyoxyalkylene alkyl ether is selected according to the above-mentioned criteria (a) to (c) according to the viscosity of the oil-containing scum, and added to the oil-containing scum, thereby separating the oil-containing scum from oil and water. It can be seen that can be promoted. Further, from the results of Experimental Examples 5 and 6, it was found that by using a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 and an alkyl group derived from a secondary alcohol, regardless of the viscosity of the oil-containing scum. It can be seen that oil-water separation of the oil-containing scum can be promoted.

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Abstract

Provided is an oil-water separation method for oil-containing scum, which is capable of separating oil and water regardless of the properties and the state of oil-containing scum. An oil-water separation method for oil-containing scum, which comprises a step wherein a polyoxyalkylene alkyl ether is selected in accordance with the viscosity of oil-containing scum based on (a)-(c) described below and the thus-selected polyoxyalkylene alkyl ether is added into the oil-containing scum. (a) In cases where the viscosity at 20°C is less than 1,000 mPa·s, a polyoxyalkylene alkyl ether having an HLB value of 10-13.5 (b) In cases where the viscosity at 20°C is 1,000 mPa·s or more but less than 2,000 mPa·s, a polyoxyalkylene alkyl ether having an HLB value of 10-13.5 and/or a polyoxyalkylene alkyl ether having an alkyl group derived from a secondary alcohol (c) In cases where the viscosity at 20°C is more than 2,000 mPa·s, a polyoxyalkylene alkyl ether having an alkyl group derived from a secondary alcohol

Description

含油スカムの油水分離方法、及び含油スカム用の油水分離剤Oil-water separation method for oil-containing scum and oil-water separation agent for oil-containing scum
　本発明は、含油スカムの油水分離方法、及び含油スカム用の油水分離剤に関する。 The present invention relates to an oil-water separation method for oil-containing scum and an oil-water separation agent for oil-containing scum.
　冷間圧延等の金属の圧延処理では、潤滑性のための油、冷却のための水が必要であり、含油排水が発生する。このように金属の圧延処理等で生じた含油排水は、油水分離槽において、水分と油分とに分離される。分離した水分は、回収して冷間圧延等で再利用するか、排水処理設備に送られる。油分は油水分離の際にスカムとして浮上する。油分を含むスカム（以下、「含油スカム」と称する）は、熱量を持つが、水分を４０～７０％程度含むため燃料としての再利用は難しい。このため含油スカムは、産業廃棄物として焼却処分されることが多い。 In the rolling process of metals such as cold rolling, oil for lubrication and water for cooling are necessary, and oil-containing wastewater is generated. Thus, the oil-containing wastewater generated by the metal rolling process or the like is separated into water and oil in the oil-water separation tank. The separated water is collected and reused by cold rolling or sent to a wastewater treatment facility. The oil floats as scum during oil-water separation. Scum containing oil (hereinafter referred to as “oil-containing scum”) has a calorific value, but contains about 40 to 70% of water, and is difficult to reuse as fuel. For this reason, oil-impregnated scum is often incinerated as industrial waste.
　含油スカムを燃料として再利用するには、含油スカム中の水分を減らす必要がある。含油排水又は含油スカムの油水分離処理としては、特許文献１～３の技術が提案されている。 In order to reuse oil-containing scum as fuel, it is necessary to reduce the moisture in the oil-containing scum. As oil-water separation treatment of oil-containing wastewater or oil-containing scum, the techniques of Patent Documents 1 to 3 have been proposed.
　特許文献１には、金属表面処理工程の脱脂工程後に発生したエマルション油等の水分含量の多い油分に対して、塩酸等の鉱酸を添加し、撹拌、静置して油水分離し、油分を燃料として再利用する方法が開示されている。
　特許文献２には、ノニオン系界面活性剤を含む含油排水に対し、該界面活性剤よりＨＬＢ値の低いノニオン系界面活性剤を添加することにより、排水を加温することなく、油相と清澄な水相とを分離する方法が開示されている。
　特許文献３には、含油廃水から油分離槽にて浮上油を分離した後、無薬注で加圧浮上槽にてさらに浮上油を分離して浮上油を２段階で除去し、その後エマルジョンブレークし凝集剤を添加して、分離された油分を凝集加圧浮上濃縮槽にてスカムとして浮上させ、浮上させたスカムを焼却処理する方法が開示されている。 In Patent Document 1, a mineral acid such as hydrochloric acid is added to an oil having a high water content such as emulsion oil generated after the degreasing process of the metal surface treatment process, and the oil is separated by stirring and standing. A method of reusing as fuel is disclosed.
In Patent Document 2, the oil phase and clarification can be obtained by adding a nonionic surfactant having an HLB value lower than that of the surfactant to the oil-containing wastewater containing the nonionic surfactant without heating the wastewater. A method for separating the aqueous phase is disclosed.
In Patent Document 3, after floating oil is separated from oil-containing wastewater in an oil separation tank, the floating oil is further separated in a pressure floating tank without chemical injection, and the floating oil is removed in two stages. A method is disclosed in which a flocculant is added, the separated oil is floated as scum in a flocculation pressurized flotation concentration tank, and the floated scum is incinerated.
特開昭５８－８４８９１号公報JP 58-84491 A 特許第４６２５８９４号公報Japanese Patent No. 4625894 特公昭４－１０３９７号公報Japanese Patent Publication No. 4-10397
　特許文献１の手法は、酸を添加するため処理設備を耐酸性とする必要があり、現有設備を使用した処理が困難であるという問題がある。
　特許文献２の手法は、含油排水に含まれている乳化剤の種類が特定できていない場合に、対応が困難であるという問題がある。また、特許文献２の手法は、含油排水の油水分離のみを考慮しており、含油排水に比べて粘度が高く、含油排水とは性状が異なる含油スカムの油水分離を全く考慮していない。
　特許文献３の手法は、三段階の処理が必要であり、設備を増設する必要があるという問題がある。また、特許文献３の手法は、含油スカムを燃料としての再利用するような高度な油水分離を考慮していない。
　さらに、冷間圧延で用いられる油や添加剤には様々な種類が存在するため、冷間圧延で生じる含油スカムは油の性状が安定しない。そして、油の性状の違いにより、油水分離剤を添加した際に油水分離できる場合と、油水分離できない場合があるが、特許文献１～３では、油の性状の違いを全く考慮していない。 The method of Patent Document 1 has a problem that it is necessary to make the treatment equipment acid-resistant because of the addition of acid, and that the treatment using the existing equipment is difficult.
The technique of Patent Document 2 has a problem that it is difficult to cope with the case where the type of emulsifier contained in the oil-containing wastewater cannot be specified. The method of Patent Document 2 considers only oil-water separation of oil-containing wastewater, and does not consider oil-water separation of oil-containing scum, which has a higher viscosity than oil-containing wastewater and has different properties from oil-containing wastewater.
The technique of Patent Document 3 requires three stages of processing and has the problem that it is necessary to add equipment. Moreover, the technique of patent document 3 does not consider the advanced oil-water separation which reuses oil-containing scum as a fuel.
Furthermore, since there are various types of oils and additives used in cold rolling, oil-containing scum generated by cold rolling does not have stable oil properties. Depending on the difference in the properties of the oil, there are cases where the oil / water separation can be performed when the oil / water separating agent is added, and there are cases where the oil / water separation cannot be performed, but Patent Documents 1 to 3 do not consider the difference in the properties of the oil at all.
　本発明は、このような状況下になされたものであり、含油スカムの性状に関わらず油水分離可能な含油スカムの油水分離方法を提供することを目的とする。また、本発明は、前記方法に用いられる油水分離剤を提供することを目的とする。 The present invention has been made under such circumstances, and an object thereof is to provide an oil-water separation method for oil-containing scum capable of oil-water separation regardless of the properties of the oil-containing scum. Moreover, an object of this invention is to provide the oil-water separation agent used for the said method.
　上記課題を解決するために、本発明は、次の［１］～［６］を提供する。
［１］含油スカムの粘度に応じて、以下の（ａ）～（ｃ）の基準によりポリオキシアルキレンアルキルエーテルを選択し、選択したポリオキシアルキレンアルキルエーテルを含油スカムに添加する工程を含む、含油スカムの油水分離方法。
（ａ）２０℃の粘度が１０００ｍＰａ・ｓ未満：ＨＬＢ値が１０～１３．５のポリオキシアルキレンアルキルエーテル
（ｂ）２０℃の粘度が１０００ｍＰａ・ｓ以上２０００ｍＰａ・ｓ未満：ＨＬＢ値が１０～１３．５のポリオキシアルキレンアルキルエーテル及び／又はアルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテル
（ｃ）２０℃の粘度が２０００ｍＰａ・ｓ以上：アルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテル
［２］ＨＬＢ値が１０～１３．５であり、かつアルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテルを含油スカムに添加する、含油スカムの油水分離方法。
［３］含油スカムが、圧延工程で発生した含油スカムである、上記［１］又は［２］に記載の含油スカムの油水分離方法。
［４］ＨＬＢ値が１０～１３．５のポリオキシアルキレンアルキルエーテルを含有してなる、圧延工程で発生した２０℃の粘度が２０００ｍＰａ・ｓ未満の含油スカム用の油水分離剤。
［５］アルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテルを含有してなる、圧延工程で発生した２０℃の粘度が１０００ｍＰａ・ｓ以上の含油スカム用の油水分離剤。
［６］ＨＬＢ値が１０～１３．５であり、かつアルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテルを含有してなる、圧延工程で発生した含油スカム用の油水分離剤。 In order to solve the above problems, the present invention provides the following [1] to [6].
[1] An oil impregnation step comprising selecting a polyoxyalkylene alkyl ether according to the following criteria (a) to (c) according to the viscosity of the oil impregnation scum and adding the selected polyoxyalkylene alkyl ether to the oil impregnation scum. Scum oil-water separation method.
(A) Viscosity at 20 ° C. of less than 1000 mPa · s: polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 (b) Viscosity at 20 ° C. of 1000 mPa · s or more and less than 2000 mPa · s: HLB value of 10 to 13 .5 polyoxyalkylene alkyl ether and / or polyoxyalkylene alkyl ether in which the alkyl group is derived from a secondary alcohol (c) a viscosity at 20 ° C. of 2000 mPa · s or more: poly from which an alkyl group is derived from a secondary alcohol Oxyalkylene alkyl ether [2] An oil-water separation method for oil-containing scum, wherein polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 and an alkyl group derived from a secondary alcohol is added to the oil-containing scum.
[3] The oil-water separation method for an oil-containing scum according to the above [1] or [2], wherein the oil-containing scum is an oil-containing scum generated in a rolling process.
[4] An oil-water separator for oil-containing scum having a viscosity at 20 ° C. of less than 2000 mPa · s generated in a rolling process, comprising a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5.
[5] An oil / water separator for oil-containing scum having a viscosity at 20 ° C. of 1000 mPa · s or more generated in a rolling process, wherein the alkyl group contains a polyoxyalkylene alkyl ether derived from a secondary alcohol.
[6] An oil-water separator for oil-impregnated scum generated in a rolling process, comprising a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 and an alkyl group derived from a secondary alcohol.
　本発明の含油スカムの油水分離方法によれば、含油スカムの性状に関わらず含油スカムを油水分離することができ、含油スカムを燃料として再利用することができる。 According to the oil-water separation method for oil-impregnated scum of the present invention, the oil-impregnated scum can be separated from water regardless of the nature of the oil-impregnated scum, and the oil-impregnated scum can be reused as fuel.
［含油スカムの油水分離方法Ａ］
　本発明の含油スカムの油水分離方法Ａは、含油スカムの粘度に応じて、以下の（ａ）～（ｃ）の基準によりポリオキシアルキレンアルキルエーテルを選択し、選択したポリオキシアルキレンアルキルエーテルを含油スカムに添加する工程を含むものである。
（ａ）２０℃の粘度が１０００ｍＰａ・ｓ未満：ＨＬＢ値が１０～１３．５のポリオキシアルキレンアルキルエーテル
（ｂ）２０℃の粘度が１０００ｍＰａ・ｓ以上２０００ｍＰａ・ｓ未満：ＨＬＢ値が１０～１３．５のポリオキシアルキレンアルキルエーテル及び／又はアルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテル
（ｃ）２０℃の粘度が２０００ｍＰａ・ｓ以上：アルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテル [Oil-containing scum oil-water separation method A]
The oil-water separation method A of the oil-impregnated scum of the present invention selects a polyoxyalkylene alkyl ether according to the following criteria (a) to (c) according to the viscosity of the oil-impregnated scum, and oils the selected polyoxyalkylene alkyl ether: It includes a step of adding to the scum.
(A) Viscosity at 20 ° C. of less than 1000 mPa · s: polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 (b) Viscosity at 20 ° C. of 1000 mPa · s or more and less than 2000 mPa · s: HLB value of 10 to 13 .5 polyoxyalkylene alkyl ether and / or polyoxyalkylene alkyl ether in which the alkyl group is derived from a secondary alcohol (c) a viscosity at 20 ° C. of 2000 mPa · s or more: poly from which an alkyl group is derived from a secondary alcohol Oxyalkylene alkyl ether
　なお、本発明でいう含油スカムとは、少なくとも油水分離槽で分離した油分（浮上油）を含むものであり、さらに場合により、油水分離時に油分とともに同時に取り出される水分等の油分以外の成分、及び含油スカムに散布する水分等の油水分離後に添加される成分を含むものである。
　本発明の含油スカムの油水分離方法に適用可能な含油スカムは特に制限されない。含油スカムの由来としては、冷間圧延等の金属の圧延処理等で生じる含油排水が挙げられる。
　含油スカム中の油分は特に限定されないが、通常３０～６０質量％である。 The oil-impregnated scum as used in the present invention includes at least the oil component (floating oil) separated in the oil-water separation tank, and, depending on the case, components other than oil components such as moisture taken out simultaneously with the oil component during oil-water separation, and It contains components added after oil-water separation, such as water sprayed on the oil-containing scum.
The oil-impregnated scum applicable to the oil-water separation method of the oil-impregnated scum of the present invention is not particularly limited. As the origin of the oil-impregnated scum, an oil-impregnated drainage generated by a metal rolling process such as cold rolling or the like can be mentioned.
The oil content in the oil-containing scum is not particularly limited, but is usually 30 to 60% by mass.
　冷間圧延で用いられる油や添加剤には様々な種類が存在するため、冷間圧延等の金属の圧延工程等の含油排水から発生する含油スカムは、油の性状が安定しない。そして、油の性状が安定しないため、含油スカムの粘度も安定しない。本発明者らは、含油スカムの粘度が油水分離の結果に大きな影響を与えることを見出し、含油スカムの粘度に応じて、以下の基準（ａ）～（ｃ）に基づいた油水分離剤を選択することにより、含油スカムの粘度に関わらず、含油スカムを油水分離することができ、含油スカムを燃料として再利用することができることを見出した。 Since there are various types of oils and additives used in cold rolling, oil-impregnated scum generated from oil-containing wastewater such as cold rolling and other metal rolling processes does not have stable oil properties. And since the properties of the oil are not stable, the viscosity of the oil-containing scum is not stable. The present inventors have found that the viscosity of oil-containing scum has a great influence on the results of oil-water separation, and selected oil-water separation agents based on the following criteria (a) to (c) according to the viscosity of oil-containing scum By doing so, it was found that the oil-containing scum can be separated into water regardless of the viscosity of the oil-containing scum, and the oil-containing scum can be reused as fuel.
　基準（ａ）
　含油スカムの２０℃の粘度が１０００ｍＰａ・ｓ未満の場合、ＨＬＢ値が１０～１３．５のポリオキシアルキレンアルキルエーテルを添加する。
　含油スカムは、油中水滴（Ｗ／Ｏ）型エマルジョンの形態を取る場合が多く、ＨＬＢ値は約３～７である。含油スカムの２０℃の粘度が１０００ｍＰａ・ｓ未満であることは、油中水滴（Ｗ／Ｏ）型エマルジョン中において、水滴が比較的動きやすい状態である。このような含油スカムに対して、ＨＬＢ値が１０～１３．５のポリオキシアルキレンアルキルエーテル（以下、「ポリオキシアルキレンアルキルエーテルａ」と称する場合がある。）を添加すると、油中水滴（Ｗ／Ｏ）型エマルジョンの成分が水と油とに分離され、油水分離効果を促進することができると考えられる。
　ＨＬＢ値が１０～１３．５のポリオキシアルキレンアルキルエーテルを用いた含油スカムの油水分離は、含油スカムの２０℃の粘度が５００ｍＰａ・ｓ以上の場合により効果的であり、８００ｍＰａ・ｓ以上の場合にさらに効果的である。 Standard (a)
When the oil-impregnated scum has a viscosity at 20 ° C. of less than 1000 mPa · s, a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 is added.
Oil-impregnated scum often takes the form of water-in-oil (W / O) emulsions, with an HLB value of about 3-7. The oil-impregnated scum having a viscosity at 20 ° C. of less than 1000 mPa · s is a state in which water droplets are relatively mobile in a water-in-oil (W / O) emulsion. When a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 (hereinafter sometimes referred to as “polyoxyalkylene alkyl ether a”) is added to such an oil-containing scum, water droplets in oil (W It is considered that the components of the / O) type emulsion are separated into water and oil, and the oil-water separation effect can be promoted.
Oil-water separation of oil-impregnated scum using polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 is more effective when the viscosity of oil-impregnated scum at 20 ° C is 500 mPa · s or more, and when it is 800 mPa · s or more It is even more effective.
　ポリオキシアルキレンアルキルエーテルａは、ＨＬＢ値が１０～１３．５であれば特に制限されない。ポリオキシアルキレンアルキルエーテルａは、例えば、アルコールに、酸化エチレン及び酸化プロピレン等のアルキレンオキシドを付加重合して得ることができ、以下の式（１）及び（２）で示すものが挙げられる。
Ｒ１－Ｏ－（Ｒ２－Ｏ）ｍ１－Ｈ　　（１）
　式（１）中、Ｒ１は炭素数８～２２の直鎖又は分岐のアルキル基を示し、Ｒ２は炭素数２又は３のアルキレン基を示し、ｍ１は２～２０の整数を示す。
Ｒ３－Ｏ－（Ｒ４－Ｏ）ｍ２－（Ｒ５－Ｏ）ｍ３－Ｈ　　（２）
　式（２）中、Ｒ３は炭素数８～２２の直鎖又は分岐のアルキル基を示し、Ｒ４は炭素数２～２０の直鎖又は分岐のアルキレン基、Ｒ５は炭素数１～１０の直鎖又は分岐のアルキレン基を示し、Ｒ４及びＲ５はそれぞれ異なり、ｍ２及びｍ３はそれぞれ０～１０の整数を示すが、ｍ２及びｍ３が同時に０となることはない。
　上記の中でも、式（１）で示すものが好ましい。また、式（１）中のＲ１の及び式（２）中のＲ３の炭素数は１０～１４が好ましく、炭素数１２がより好ましい。また、式（１）中のＲ２の炭素数は２であることが好ましい。 The polyoxyalkylene alkyl ether a is not particularly limited as long as it has an HLB value of 10 to 13.5. The polyoxyalkylene alkyl ether a can be obtained, for example, by addition polymerization of an alkylene oxide such as ethylene oxide and propylene oxide to an alcohol, and examples thereof include those represented by the following formulas (1) and (2).
R 1 —O— (R 2 —O) m1 —H (1)
In the formula (1), R 1 represents a linear or branched alkyl group having 8 to 22 carbon atoms, R 2 represents an alkylene group having 2 or 3 carbon atoms, and m1 represents an integer of 2 to 20.
R 3 —O— (R 4 —O) m2 — (R 5 —O) m3 —H (2)
In the formula (2), R 3 represents a linear or branched alkyl group having 8 to 22 carbon atoms, R 4 represents a linear or branched alkylene group having 2 to 20 carbon atoms, and R 5 represents a carbon number of 1 to 10 R 4 and R 5 are different from each other, m2 and m3 each represent an integer of 0 to 10, but m2 and m3 are not 0 at the same time.
Among the above, those represented by the formula (1) are preferable. Further, the carbon number of R 1 in the formula (1) and R 3 in the formula (2) is preferably 10 to 14, more preferably 12 carbon atoms. The number of carbon atoms of R 2 in the formula (1) is preferably 2.
　基準（ｃ）
　含油スカムの２０℃の粘度が２０００ｍＰａ・ｓ以上の場合、アルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテルを添加する。
　含油スカムの２０℃の粘度が２０００ｍＰａ・ｓ以上であることは、油中水滴（Ｗ／Ｏ）型エマルジョン中において水滴の動きが制限された状態である。このような含油スカムに対して、アルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテル（以下、「ポリオキシアルキレンアルキルエーテルｂ」と称する場合がある。）を添加すると、油中水滴（Ｗ／Ｏ）型エマルジョンの成分が水と油とに分離され、油水分離効果を促進することができると考えられる。
　アルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテルを用いた含油スカムの油水分離は、含油スカムの２０℃の粘度が３０００～１００００ｍＰａ・ｓの場合により効果的であり、５５００～７０００ｍＰａ・ｓの場合にさらに効果的である。 Standard (c)
When the viscosity of the oil-containing scum at 20 ° C. is 2000 mPa · s or more, a polyoxyalkylene alkyl ether whose alkyl group is derived from a secondary alcohol is added.
The oil-impregnated scum having a viscosity at 20 ° C. of 2000 mPa · s or more is a state where movement of water droplets is restricted in a water-in-oil (W / O) emulsion. When a polyoxyalkylene alkyl ether having an alkyl group derived from a secondary alcohol (hereinafter sometimes referred to as “polyoxyalkylene alkyl ether b”) is added to such an oil-containing scum, water droplets in oil ( It is considered that the components of the (W / O) type emulsion are separated into water and oil, and the oil / water separation effect can be promoted.
Oil-water separation of oil-containing scum using a polyoxyalkylene alkyl ether whose alkyl group is derived from a secondary alcohol is more effective when the oil-containing scum has a viscosity at 20 ° C. of 3000 to 10,000 mPa · s, and 5500 to 7000 mPa · s. It is more effective in the case of s.
　ポリオキシアルキレンアルキルエーテルｂは、アルキル基が第二級アルコールに由来するものであれば特に制限されない。ポリオキシアルキレンアルキルエーテルｂは、例えば、第二級アルコールに、酸化エチレン及び酸化プロピレン等のアルキレンオキシドを付加重合して得ることができ、以下の式（３）及び（４）で示すものが挙げられる。
Ｒ６－Ｏ－（Ｒ７－Ｏ）ｍ４－Ｈ　　（３）
　式（３）中、Ｒ６は炭素数８～２２の分岐のアルキル基を示し、Ｒ７は炭素数２又は３のアルキレン基を示し、ｍ４は２～２０の整数を示す。
Ｒ８－Ｏ－（Ｒ９－Ｏ）ｍ５－（Ｒ１０－Ｏ）ｍ６－Ｈ　　（４）
　式（４）中、Ｒ８は炭素数８～２２の分岐のアルキル基を示し、Ｒ９は炭素数２～２０の直鎖又は分岐のアルキレン基、Ｒ１０は炭素数１～１０の直鎖又は分岐のアルキレン基を示し、Ｒ９及びＲ１０はそれぞれ異なり、ｍ５及びｍ６はそれぞれ０～１０の整数を示すが、ｍ５及びｍ６が同時に０となることはない。
　上記の中でも、式（３）で示すものが好ましい。また、式（３）中のＲ６の及び式（４）中のＲ８の炭素数は１０～１４が好ましく、炭素数１２がより好ましい。また、式（３）中のＲ７の炭素数は２であることが好ましい。 The polyoxyalkylene alkyl ether b is not particularly limited as long as the alkyl group is derived from a secondary alcohol. The polyoxyalkylene alkyl ether b can be obtained, for example, by addition polymerization of an alkylene oxide such as ethylene oxide and propylene oxide to a secondary alcohol, and examples thereof include those represented by the following formulas (3) and (4). It is done.
R 6 —O— (R 7 —O) m4 —H (3)
In the formula (3), R 6 represents a branched alkyl group having 8 to 22 carbon atoms, R 7 represents an alkylene group having 2 or 3 carbon atoms, and m4 represents an integer of 2 to 20.
R 8 —O— (R 9 —O) m5 — (R 10 —O) m6 —H (4)
In the formula (4), R 8 represents a branched alkyl group having 8 to 22 carbon atoms, R 9 is a linear or branched alkylene group having 2 to 20 carbon atoms, and R 10 is a linear chain having 1 to 10 carbon atoms. Or a branched alkylene group, R 9 and R 10 are different from each other, and m5 and m6 each represent an integer of 0 to 10, but m5 and m6 are not 0 at the same time.
Among the above, those represented by the formula (3) are preferable. Further, the carbon number of R 6 in the formula (3) and R 8 in the formula (4) is preferably 10 to 14, more preferably 12 carbon atoms. The number of carbon atoms of R 7 in the formula (3) is preferably 2.
　基準（ｂ）
　含油スカムの２０℃の粘度が１０００ｍＰａ・ｓ以上２０００ｍＰａ・ｓ未満の場合、ＨＬＢ値が１０～１３．５のポリオキシアルキレンアルキルエーテル及び／又はアルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテルを添加する。
　含油スカムの２０℃の粘度が１０００ｍＰａ・ｓ以上２０００ｍＰａ・ｓ未満であることは、含油スカム中の油分が、基準（ａ）のスカムの油分と、基準（ｃ）のスカムの油分との中間の性状を示すこと、言い換えると、油中水滴（Ｗ／Ｏ）型エマルジョン中における水滴の動きやすさが、基準（ａ）と基準（ｃ）との中間であることを意味する。このような中間領域では、ポリオキシアルキレンアルキルエーテルａ及び／又はポリオキシアルキレンアルキルエーテルｂの何れも油水分離効果を発揮できる。
　基準（ｂ）のポリオキシアルキレンアルキルエーテルとしては、基準（ａ）で例示したポリオキシアルキレンアルキルエーテル及び／又は基準（ｂ）で例示したポリオキシアルキレンアルキルエーテルを用いることができる。 Standard (b)
When the oil-containing scum has a viscosity at 20 ° C. of 1000 mPa · s or more and less than 2000 mPa · s, a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 and / or an alkyl group derived from a secondary alcohol Add ether.
The oil-impregnated scum having a viscosity at 20 ° C. of 1000 mPa · s or more and less than 2000 mPa · s means that the oil content in the oil-containing scum is intermediate between the oil content of the scum of the reference (a) and the oil content of the scum of the reference (c). It indicates the property, in other words, the ease of movement of the water droplets in the water-in-oil (W / O) type emulsion is intermediate between the criteria (a) and the criteria (c). In such an intermediate region, both the polyoxyalkylene alkyl ether a and / or the polyoxyalkylene alkyl ether b can exhibit the oil-water separation effect.
As the polyoxyalkylene alkyl ether of the standard (b), the polyoxyalkylene alkyl ether exemplified in the standard (a) and / or the polyoxyalkylene alkyl ether exemplified in the standard (b) can be used.
　なお、含油スカムの２０℃の粘度が１０００ｍＰａ・ｓ以上２０００ｍＰａ・ｓ未満の領域をあえて区分けすると、含油スカムの２０℃の粘度が１０００ｍＰａ・ｓ以上１５００ｍＰａ・ｓ以下の場合は、ＨＬＢ値が１０～１３．５のポリオキシアルキレンアルキルエーテルを添加することが好ましく、含油スカムの２０℃の粘度が１５００ｍＰａ・ｓ超２０００ｍＰａ・ｓ未満の場合は、ＨＬＢ値が１０～１３．５のポリオキシアルキレンアルキルエーテル及び／又はアルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテルを添加することが好ましい。 When the oil-impregnated scum has a viscosity at 20 ° C. of 1000 mPa · s or more and less than 2000 mPa · s, the HLB value is 10 to 10 when the oil-impregnated scum has a viscosity at 20 ° C. of 1000 mPa · s to 1500 mPa · s. It is preferable to add 13.5 polyoxyalkylene alkyl ether, and when the oil-containing scum has a viscosity at 20 ° C. of more than 1500 mPa · s and less than 2000 mPa · s, the polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 It is also preferable to add polyoxyalkylene alkyl ethers whose alkyl groups are derived from secondary alcohols.
（事前工程）
　なお、油水分離剤の選択に先立って、含油スカムの２０℃の粘度を算出する工程を行い、算出した粘度に応じて、基準（ａ）～（ｃ）の油水分離剤を選択することも有用である。 (Preliminary process)
Prior to the selection of the oil / water separator, it is also useful to perform a step of calculating the viscosity of the oil-containing scum at 20 ° C., and to select the oil / water separator of criteria (a) to (c) according to the calculated viscosity. It is.
　含油スカムの２０℃の粘度を算出する方法は、（１）２０℃に調整した含油スカムの粘度を測定する方法、（２）他の温度（例えば、含油スカム採取時の温度、室温で３０分放置した含油スカムの温度等）で数点含油スカムの粘度を測定し、ｌｎη－１／Ｔの片対数にプロットして得られる直線から算出する方法、（３）含油スカムの組成が分かる場合には、アンドレーの式等の粘度算出式により算出する方法が挙げられる。 The method for calculating the viscosity of oil-impregnated scum at 20 ° C. is as follows: (1) Method of measuring the viscosity of oil-impregnated scum adjusted to 20 ° C., (2) Other temperature (for example, temperature at the time of collecting oil-impregnated scum, 30 minutes at room temperature The temperature of the oil-impregnated scum that has been left standing, etc.), and calculating the viscosity of the oil-impregnated scum from a straight line obtained by plotting the logarithm of lnη-1 / T. (3) When the composition of the oil-impregnated scum is known May be calculated by a viscosity calculation formula such as Andre's formula.
［含油スカムの油水分離方法Ｂ］
　本発明の含油スカムの油水分離方法Ｂは、ＨＬＢ値が１０～１３．５であり、かつアルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテルを含油スカムに添加するものである。 [Oil-containing scum oil-water separation method B]
In the oil-water separation method B of the oil-containing scum of the present invention, a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 and an alkyl group derived from a secondary alcohol is added to the oil-containing scum.
　含油スカムの油水分離方法Ａで述べたように、含油スカムの２０℃の粘度が１０００ｍＰａ・ｓ未満の場合は、ポリオキシアルキレンアルキルエーテルａが油水分離に有効であり、含油スカムの２０℃の粘度が１０００ｍＰａ・ｓ以上２０００ｍＰａ・ｓ未満の場合は、ポリオキシアルキレンアルキルエーテルａ及び／又はポリオキシアルキレンアルキルエーテルｂが油水分離に有効であり、含油スカムの２０℃の粘度が２０００ｍＰａ・ｓ以上の場合は、ポリオキシアルキレンアルキルエーテルｂが油水分離に有効である。
　したがって、ＨＬＢ値が１０～１３．５であり、かつアルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテル（以下、「ポリオキシアルキレンアルキルエーテルｃ」と称する場合がある。）は、ポリオキシアルキレンアルキルエーテルａ及びポリオキシアルキレンアルキルエーテルｂの両方の性質を備え、含油スカムの粘度に関わらず油水分離効果を発揮できる。 As described in the oil-water separation method A of the oil-containing scum, when the viscosity of the oil-containing scum is 20 ° C. is less than 1000 mPa · s, the polyoxyalkylene alkyl ether a is effective for oil-water separation, and the viscosity of the oil-containing scum of 20 ° C. Is 1000 mPa · s or more and less than 2000 mPa · s, polyoxyalkylene alkyl ether a and / or polyoxyalkylene alkyl ether b is effective for oil-water separation, and the viscosity of oil-containing scum at 20 ° C. is 2000 mPa · s or more. The polyoxyalkylene alkyl ether b is effective for oil-water separation.
Accordingly, a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 and an alkyl group derived from a secondary alcohol (hereinafter sometimes referred to as “polyoxyalkylene alkyl ether c”) is a polyoxyalkylene alkyl ether. It has both the properties of oxyalkylene alkyl ether a and polyoxyalkylene alkyl ether b, and can exhibit an oil-water separation effect regardless of the viscosity of the oil-containing scum.
　ポリオキシアルキレンアルキルエーテルｃは、例えば、第二級アルコールに、酸化エチレン及び酸化プロピレン等のアルキレンオキシドを付加重合して得ることができ、以下の式（５）及び（６）で示すものが挙げられる。
Ｒ１１－Ｏ－（Ｒ１２－Ｏ）ｍ７－Ｈ　　（５）
　式（５）中、Ｒ１１は炭素数８～２２の分岐のアルキル基を示し、Ｒ１２は炭素数２又は３のアルキレン基を示し、ｍ７は２～２０の整数を示す。
Ｒ１３－Ｏ－（Ｒ１４－Ｏ）ｍ８－（Ｒ１５－Ｏ）ｍ９－Ｈ　　（６）
　式（６）中、Ｒ１３は炭素数８～２２の分岐のアルキル基を示し、Ｒ１４は炭素数２～２０の直鎖又は分岐のアルキレン基、Ｒ１５は炭素数１～１０の直鎖又は分岐のアルキレン基を示し、Ｒ１４及びＲ１５はそれぞれ異なり、ｍ８及びｍ９はそれぞれ０～１０の整数を示すが、ｍ８及びｍ９が同時に０となることはない。
　上記の中でも、式（５）で示すものが好ましい。また、式（５）中のＲ１１の及び式（６）中のＲ１３の炭素数は１０～１４が好ましく、炭素数１２がより好ましい。また、式（５）中のＲ１２の炭素数は２であることが好ましい。 The polyoxyalkylene alkyl ether c can be obtained, for example, by addition polymerization of a secondary alcohol with an alkylene oxide such as ethylene oxide or propylene oxide, and those represented by the following formulas (5) and (6) are mentioned. It is done.
R 11 —O— (R 12 —O) m7 —H (5)
In the formula (5), R 11 represents a branched alkyl group having 8 to 22 carbon atoms, R 12 represents an alkylene group having 2 or 3 carbon atoms, and m7 represents an integer of 2 to 20.
R 13 —O— (R 14 —O) m8 — (R 15 —O) m9 —H (6)
In the formula (6), R 13 represents a branched alkyl group having 8 to 22 carbon atoms, R 14 is a linear or branched alkylene group having 2 to 20 carbon atoms, and R 15 is a straight chain having 1 to 10 carbon atoms. Or a branched alkylene group, R 14 and R 15 are different from each other, and m8 and m9 each represent an integer of 0 to 10, but m8 and m9 are not 0 simultaneously.
Among the above, those represented by the formula (5) are preferable. Further, the carbon number of R 11 in formula (5) and R 13 in formula (6) is preferably 10 to 14, and more preferably 12 carbon atoms. The number of carbon atoms of R 12 in the formula (5) is preferably 2.
　含油スカムの油水分離方法Ｂにおける含油スカムの粘度は特に制限されないが、含油スカムの２０℃の粘度が５００～１００００ｍＰａ・ｓの場合により効果的であり、８００～７０００ｍＰａ・ｓの場合にさらに効果的である。 The viscosity of the oil-impregnated scum in the oil-water separation method B of the oil-impregnated scum is not particularly limited, but is more effective when the oil-impregnated scum has a viscosity at 20 ° C. of 500 to 10,000 mPa · s, and more effective when the viscosity is 800 to 7000 mPa · s. It is.
＜ポリオキシアルキレンアルキルエーテルの添加の諸条件＞
　含油スカムの油水分離方法Ａ及びＢともに、ポリオキシアルキレンアルキルエーテルは、含油スカム中に対して５ｇ／Ｌ～２０ｇ／Ｌ添加することが好ましく、１０～１５ｇ／Ｌ添加することがより好ましい。ポリオキシアルキレンアルキルエーテルを２種類以上用いる場合、ポリオキシアルキレンアルキルエーテルの合計添加量を前記範囲とすればよい。 <Conditions for addition of polyoxyalkylene alkyl ether>
In both oil-water separation methods A and B of the oil-containing scum, the polyoxyalkylene alkyl ether is preferably added in an amount of 5 to 20 g / L, more preferably 10 to 15 g / L, based on the oil-containing scum. When two or more types of polyoxyalkylene alkyl ethers are used, the total amount of polyoxyalkylene alkyl ethers may be set within the above range.
　含油スカムの油水分離方法Ａ及びＢともに、ポリオキシアルキレンアルキルエーテルを添加する際の形態は、そのまま添加しても良いし、溶剤や水等の溶媒で希釈して添加してもよい。希釈液中のポリオキシアルキレンアルキルエーテルの濃度は１０～９５質量％とすることが好ましい。 In both the oil-water separation methods A and B of the oil-containing scum, the form of adding the polyoxyalkylene alkyl ether may be added as it is, or may be added after being diluted with a solvent such as a solvent or water. The concentration of the polyoxyalkylene alkyl ether in the diluted solution is preferably 10 to 95% by mass.
　含油スカムの油水分離方法Ａ及びＢともに、ポリオキシアルキレンアルキルエーテルを添加する箇所は特に制限されない。添加箇所としては、例えば、加圧浮上槽、加圧浮上槽から含油スカムを移送する配管、加圧浮上槽から移送した含油スカムを貯留する槽等が挙げられる。また、含油排水にポリオキシアルキレンアルキルエーテルを添加することも有効である。 In both oil-water separation methods A and B of the oil-containing scum, there are no particular restrictions on the location where the polyoxyalkylene alkyl ether is added. Examples of the location of addition include a pressurized floating tank, a pipe for transferring the oil-containing scum from the pressurized floating tank, and a tank for storing the oil-containing scum transferred from the pressurized floating tank. It is also effective to add polyoxyalkylene alkyl ether to the oil-containing wastewater.
　含油スカムの油水分離方法Ａ及びＢともに、含油スカムや含油排水にポリオキシアルキレンアルキルエーテルを添加した後は、撹拌を行い静置する。攪拌後にすぐに油水分離する場合もあり、静置は数分程度でもよいが、大抵は１日程度静置すれば油水分離は完了する。
　ポリオキシアルキレンアルキルエーテルを添加する際の含油スカムの温度及びｐＨは特に制限されない。温度は５～７０℃が好ましく、２５～３５℃がより好ましく、３０℃が特に好ましい。ｐＨは５～９が好ましく、６～７がより好ましく、６．５が特に好ましい。 In both oil-water separation methods A and B of the oil-containing scum, after the polyoxyalkylene alkyl ether is added to the oil-containing scum or oil-containing wastewater, the mixture is stirred and allowed to stand. Oil-water separation may be performed immediately after stirring, and may be allowed to stand for several minutes, but in most cases, the oil-water separation is completed if the mixture is left standing for about one day.
The temperature and pH of the oil-containing scum when adding the polyoxyalkylene alkyl ether are not particularly limited. The temperature is preferably 5 to 70 ° C, more preferably 25 to 35 ° C, and particularly preferably 30 ° C. The pH is preferably 5 to 9, more preferably 6 to 7, and particularly preferably 6.5.
＜任意添加成分＞
　含油スカムの油水分離方法Ａ及びＢともに、本発明の目的が損なわれない範囲で、各種の添加成分、例えば、アニオン系界面活性剤、カチオン系界面活性剤等を添加することできる。これらの添加成分は一種単独で又は二種以上を組み合わせて用いることができる。 <Optional components>
In both oil-water separation methods A and B of the oil-containing scum, various additive components such as an anionic surfactant and a cationic surfactant can be added without departing from the object of the present invention. These additive components can be used alone or in combination of two or more.
［含油スカム用の油水分離剤Ａ］
　本発明の含油スカム用の油水分離剤Ａは、ＨＬＢ値が１０～１３．５のポリオキシアルキレンアルキルエーテルを含有してなる、圧延工程で発生した２０℃の粘度が２０００ｍＰａ・ｓ未満の含油スカム用の油水分離剤である。
　すなわち、油水分離剤Ａは、上述したポリオキシアルキレンアルキルエーテルａを含有してなるものである。 [Oil-water separator A for oil-impregnated scum]
The oil / water separator A for oil-impregnated scum of the present invention comprises a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5, and the oil-impregnated scum having a viscosity at 20 ° C. of less than 2000 mPa · s generated in the rolling process. It is an oil-water separator for use.
That is, the oil / water separator A contains the polyoxyalkylene alkyl ether a described above.
　油水分離剤Ａ中には、ポリオキシアルキレンアルキルエーテルａ以外の成分を含有しても良いが、油水分離剤Ａの全固形分中のポリオキシアルキレンアルキルエーテルａが８０質量％以上であることが好ましく、９０質量％以上であることがより好ましく、１００質量％であることがさらに好ましい。
　油水分離剤Ａは、含油スカムの２０℃の粘度が５００ｍＰａ・ｓ以上１５００ｍＰａ・ｓ以下の場合により効果的であり、８００ｍＰａ・ｓ以上１５００ｍＰａ・ｓ以下の場合にさらに効果的である。 The oil / water separating agent A may contain components other than the polyoxyalkylene alkyl ether a, but the polyoxyalkylene alkyl ether a in the total solid content of the oil / water separating agent A may be 80% by mass or more. Preferably, the content is 90% by mass or more, and more preferably 100% by mass.
The oil / water separator A is more effective when the viscosity of the oil-containing scum at 20 ° C. is 500 mPa · s or more and 1500 mPa · s or less, and more effective when the viscosity is 800 mPa · s or more and 1500 mPa · s or less.
［含油スカム用の油水分離剤Ｂ］
　本発明の含油スカム用の油水分離剤Ｂは、アルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテルを含有してなる、圧延工程で発生した２０℃の粘度が１０００ｍＰａ・ｓ以上の含油スカム用の油水分離剤である。
　すなわち、油水分離剤Ｂは、上述したポリオキシアルキレンアルキルエーテルｂを含有してなるものである。 [Oil / water separator B for oil-impregnated scum]
The oil / water separating agent B for oil-impregnated scum of the present invention comprises a polyoxyalkylene alkyl ether having an alkyl group derived from a secondary alcohol, and has an oil-impregnating viscosity at 20 ° C. of 1000 mPa · s or more generated in a rolling process. Oil / water separator for scum.
That is, the oil / water separator B contains the polyoxyalkylene alkyl ether b described above.
　油水分離剤Ｂ中には、ポリオキシアルキレンアルキルエーテルｂ以外の成分を含有しても良いが、油水分離剤Ｂの全固形分中のポリオキシアルキレンアルキルエーテルｂが８０質量％以上であることが好ましく、９０質量％以上であることがより好ましく、１００質量％であることがさらに好ましい。
　油水分離剤Ｂは、含油スカムの２０℃の粘度が１３００ｍＰａ・ｓ以上１００００ｍＰａ・ｓ以下の場合により効果的であり、１５００ｍＰａ・ｓ超８００００ｍＰａ・ｓの場合にさらに効果的であり、５５００ｍＰａ・ｓ以上７０００ｍＰａ・ｓ以下の場合によりさらに効果的である。 The oil / water separating agent B may contain components other than the polyoxyalkylene alkyl ether b, but the polyoxyalkylene alkyl ether b in the total solid content of the oil / water separating agent B is 80% by mass or more. Preferably, the content is 90% by mass or more, and more preferably 100% by mass.
The oil / water separating agent B is more effective when the viscosity of the oil-containing scum at 20 ° C. is 1300 mPa · s or more and 10,000 mPa · s or less, and more effective when the viscosity is 1500 mPa · s or more and 80000 mPa · s, and 5500 mPa · s or more. Even more effective in the case of 7000 mPa · s or less.
［含油スカム用の油水分離剤Ｃ］
　本発明の含油スカム用の油水分離剤Ｃは、ＨＬＢ値が１０～１３．５であり、かつアルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテルを含有してなる、圧延工程で発生した含油スカム用の油水分離剤である。
　すなわち、油水分離剤Ｃは、上述したポリオキシアルキレンアルキルエーテルｃを含有してなるものである。 [Oil / water separator C for oil-containing scum]
The oil / water separating agent C for oil-impregnated scum of the present invention is generated in a rolling process, having an HLB value of 10 to 13.5 and containing a polyoxyalkylene alkyl ether having an alkyl group derived from a secondary alcohol. It is an oil-water separator for oil-impregnated scum.
That is, the oil / water separator C contains the polyoxyalkylene alkyl ether c described above.
　油水分離剤Ｃ中には、ポリオキシアルキレンアルキルエーテルｃ以外の成分を含有しても良いが、油水分離剤Ｃの全固形分中のポリオキシアルキレンアルキルエーテルｃが８０質量％以上であることが好ましく、９０質量％以上であることがより好ましく、１００質量％であることがさらに好ましい。 The oil / water separating agent C may contain components other than the polyoxyalkylene alkyl ether c, but the polyoxyalkylene alkyl ether c in the total solid content of the oil / water separating agent C may be 80% by mass or more. Preferably, the content is 90% by mass or more, and more preferably 100% by mass.
　油水分離剤Ｃは、含油スカムの２０℃の粘度が５００～１００００ｍＰａ・ｓの場合により効果的であり、８００～７０００ｍＰａ・ｓの場合にさらに効果的である。 The oil / water separator C is more effective when the viscosity of the oil-containing scum at 20 ° C. is 500 to 10,000 mPa · s, and more effective when the viscosity is 800 to 7000 mPa · s.
　次に、本発明を実施例により更に詳細に説明するが、本発明はこれらの例によって何ら限定されるものではない。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
１．含油スカムの粘度測定
　冷間圧延を経た含油排水の油水分離槽で採取した４種類の含油スカム（含油スカム１～４）を、２０℃に設定した恒温槽で、Ｂ型粘度計を使用し、ローターＮｏ．６、４０ｒｐｍの条件で測定した。結果を以下に示す。
スカム１：粘度９５０ｍＰａ・ｓ
スカム２：粘度１４００ｍＰａ・ｓ
スカム３：粘度６６００ｍＰａ・ｓ
スカム４：粘度６０００ｍＰａ・ｓ 1. Viscosity measurement of oil-impregnated scum Four types of oil-impregnated scum (oil-impregnated scum 1 to 4) collected in an oil-water separation tank of oil-impregnated wastewater that has undergone cold rolling are used in a thermostat set at 20 ° C, using a B-type viscometer, Rotor No. The measurement was performed at 6, 40 rpm. The results are shown below.
Scum 1: Viscosity 950 mPa · s
Scum 2: Viscosity 1400 mPa · s
Scum 3: Viscosity 6600 mPa · s
Scum 4: Viscosity 6000 mPa · s
２．含油スカムの油水分離効果の確認
２－１．油水分離前の含油スカム中の水分濃度の算出
　ＪＩＳ　Ｋ－２２７５の蒸留法に準拠して、含油スカム中の水分量を測定し、水分濃度を算出した。
２－２．油水分離後の含油スカムの水分濃度の算出
　含油スカムを入れた缶を３０～４０回撹拌混合した。攪拌後の含油スカムを１００ｍｌの試験管に１００ｍｌ注ぎ、薬剤（ポリオキシアルキレンアルキルエーテル）の濃度が１０ｇ／Ｌとなるように薬剤を添加した。試験管内の試料をスパチュラで１２０秒攪拌し、含油スカムと薬剤とを混合した。３０℃の恒温槽で１日静置後、水相の高さから分離した水分量を測定し、含油スカムに残存している水分濃度を算出した。
　含油スカムと薬剤とは表１及び２の組み合わせで行った。
２－３．油水分離処理による含油スカムの水分低減率の算出
　油水分離前の含油スカム中の水分濃度を「Ｘ％」、油水分離後の含油スカムの水分濃度を「Ｙ％」とし、下記式により油水分離処理による含油スカムの水分低減率を算出した。水分低減率が５０％以上のものを「Ａ」、３０％以上５０％未満のものを「Ｂ」、３０％未満のものを「Ｃ」とした。結果を表１及び２に示す。
　含油スカムの水分低減率（％）＝［（Ｘ－Ｙ）／Ｘ］×１００ 2. 2. Confirmation of oil / water separation effect of oil-impregnated scum 2-1. Calculation of water concentration in oil-containing scum before oil-water separation According to the distillation method of JIS K-2275, the amount of water in oil-containing scum was measured and the water concentration was calculated.
2-2. Calculation of water concentration of oil-impregnated scum after oil-water separation The can containing the oil-impregnated scum was stirred and mixed 30 to 40 times. 100 ml of the oil-impregnated scum after stirring was poured into a 100 ml test tube, and the drug was added so that the drug (polyoxyalkylene alkyl ether) concentration was 10 g / L. The sample in the test tube was stirred with a spatula for 120 seconds to mix the oil-containing scum and the drug. After standing in a thermostatic bath at 30 ° C. for one day, the amount of water separated from the height of the aqueous phase was measured, and the water concentration remaining in the oil-containing scum was calculated.
The oil-impregnated scum and the chemical were used in the combinations shown in Tables 1 and 2.
2-3. Calculation of moisture reduction rate of oil-impregnated scum by oil-water separation treatment The water concentration in the oil-impregnated scum before oil-water separation is “X%”, and the water concentration of the oil-impregnated scum after oil-water separation is “Y%”. The moisture reduction rate of the oil-impregnated scum was calculated. A sample having a moisture reduction rate of 50% or more was designated “A”, a sample having a moisture reduction rate of 30% or more and less than 50% was designated “B”, and a sample having a moisture reduction rate of less than 30% was designated “C”. The results are shown in Tables 1 and 2.
Moisture reduction rate of oil-impregnated scum (%) = [(XY) / X] × 100
３．使用薬剤
薬剤１：ノニオン系界面活性剤（ポリオキシエチレンラウリルエーテル；三洋化成工業社製、エマルミンNL-70；ＨＬＢ値１２．４）
薬剤２：ノニオン系界面活性剤（ポリオキシアルキレンアルキルエーテル；三洋化成工業社製、ナロアクティーCL-85；ＨＬＢ値１２．６）
薬剤３：ノニオン系界面活性剤（ポリオキシエチレンオレイルエーテルとポリオキシエチレンセチルエーテルの混合物；三洋化成工業社製、エマルミン110；ＨＬＢ値１３．２）
薬剤４：ノニオン系界面活性剤（ポリオキシエチレンアルキルエーテル；三洋化成工業社製、セドランSF-506；ＨＬＢ値６．１）
薬剤５：ノニオン系界面活性剤（ポリオキシエチレンアルキルエーテル；三洋化成工業社製、サンノニックSS-50；ＨＬＢ値１０．５）
薬剤６：ノニオン系界面活性剤（ポリオキシエチレンアルキルエーテル；三洋化成工業社製、サンノニックSS-90；ＨＬＢ値１３．２）
薬剤７：ノニオン系界面活性剤（ポリオキシエチレンアルキルエーテル；三洋化成工業社製、ナロアクティーCL-40；ＨＬＢ値８．９）
薬剤８：ノニオン系界面活性剤（ポリオキシアルキレンアルキルエーテル；三洋化成工業社製、ナロアクティーID-40；ＨＬＢ値８．１）
薬剤９：ノニオン系界面活性剤（ポリオキシエチレンオレイルエーテルとポリオキシエチレンセチルエーテルの混合物；三洋化成工業社製、エマルミン40；ＨＬＢ値８．０）
薬剤10：アニオン系界面活性剤（ポリオキシエチレンアルキルスルホコハク酸二ナトリウム；三洋化成工業社製、ビューライトESS）
薬剤11：アニオン系界面活性剤（ポリオキシアルキレンアルキルスルホコハク酸二ナトリウム；三洋化成工業社製、サンモリンOT-70）
薬剤12：カチオン系界面活性剤（塩化ステアリルジメチルベンジルアンモニウム；三洋化成工業株式会社製、カチオンS）
薬剤13：カチオン系界面活性剤（塩化ベヘニルトリメチルアンモニウム；三洋化成工業株式会社製、エコノールTM-22） 3. Drugs used 1: Nonionic surfactant (polyoxyethylene lauryl ether; manufactured by Sanyo Chemical Industries, Emalmin NL-70; HLB value 12.4)
Agent 2: Nonionic surfactant (polyoxyalkylene alkyl ether; manufactured by Sanyo Chemical Industries, NAROACTY CL-85; HLB value 12.6)
Agent 3: Nonionic surfactant (mixture of polyoxyethylene oleyl ether and polyoxyethylene cetyl ether; manufactured by Sanyo Chemical Industries, Emalmin 110; HLB value 13.2)
Agent 4: Nonionic surfactant (polyoxyethylene alkyl ether; manufactured by Sanyo Chemical Industries, Cedran SF-506; HLB value 6.1)
Agent 5: Nonionic surfactant (polyoxyethylene alkyl ether; Sanyo Chemical Industries, Sannonic SS-50; HLB value 10.5)
Agent 6: Nonionic surfactant (polyoxyethylene alkyl ether; Sanyo Chemical Industries, Sannonic SS-90; HLB value 13.2)
Agent 7: Nonionic surfactant (polyoxyethylene alkyl ether; manufactured by Sanyo Chemical Industries, NAROACTY CL-40; HLB value 8.9)
Agent 8: Nonionic surfactant (polyoxyalkylene alkyl ether; manufactured by Sanyo Chemical Industries, NAROACTY ID-40; HLB value 8.1)
Agent 9: Nonionic surfactant (polyoxyethylene oleyl ether and polyoxyethylene cetyl ether mixture; Sanyo Chemical Industries, Emalmin 40; HLB value 8.0)
Drug 10: Anionic surfactant (polyoxyethylene alkylsulfosuccinate disodium; manufactured by Sanyo Chemical Industries, Burelite ESS)
Agent 11: Anionic surfactant (polyoxyalkylene alkyl sulfosuccinate disodium; Sanyo Kasei Kogyo Co., Ltd., Sanmorin OT-70)
Agent 12: Cationic surfactant (stearyldimethylbenzylammonium chloride; manufactured by Sanyo Chemical Industries, Ltd., Cation S)
Agent 13: Cationic surfactant (behenyltrimethylammonium chloride; manufactured by Sanyo Chemical Industries, Econol TM-22)
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１及び２の結果から、含油スカムの粘度に応じて、上述の（ａ）～（ｃ）の基準によりポリオキシアルキレンアルキルエーテルを選択し、含油スカムに添加することにより、含油スカムの油水分離を促進できることが分かる。
　また、実験例５及び６の結果から、ＨＬＢ値が１０～１３．５であり、かつアルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテルを用いることにより、含油スカムの粘度に関わらず、含油スカムの油水分離を促進できることが分かる。 From the results of Tables 1 and 2, the polyoxyalkylene alkyl ether is selected according to the above-mentioned criteria (a) to (c) according to the viscosity of the oil-containing scum, and added to the oil-containing scum, thereby separating the oil-containing scum from oil and water. It can be seen that can be promoted.
Further, from the results of Experimental Examples 5 and 6, it was found that by using a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 and an alkyl group derived from a secondary alcohol, regardless of the viscosity of the oil-containing scum. It can be seen that oil-water separation of the oil-containing scum can be promoted.

Claims (6)

  1. 　含油スカムの粘度に応じて、以下の（ａ）～（ｃ）の基準によりポリオキシアルキレンアルキルエーテルを選択し、選択したポリオキシアルキレンアルキルエーテルを含油スカムに添加する工程を含む、含油スカムの油水分離方法。
    （ａ）２０℃の粘度が１０００ｍＰａ・ｓ未満：ＨＬＢ値が１０～１３．５のポリオキシアルキレンアルキルエーテル
    （ｂ）２０℃の粘度が１０００ｍＰａ・ｓ以上２０００ｍＰａ・ｓ未満：ＨＬＢ値が１０～１３．５のポリオキシアルキレンアルキルエーテル及び／又はアルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテル
    （ｃ）２０℃の粘度が２０００ｍＰａ・ｓ以上：アルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテル     According to the viscosity of the oil-containing scum, the polyoxyalkylene alkyl ether is selected according to the following criteria (a) to (c), and the selected polyoxyalkylene alkyl ether is added to the oil-containing scum. Separation method.
    (A) Viscosity at 20 ° C. of less than 1000 mPa · s: polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 (b) Viscosity at 20 ° C. of 1000 mPa · s or more and less than 2000 mPa · s: HLB value of 10 to 13 .5 polyoxyalkylene alkyl ether and / or polyoxyalkylene alkyl ether in which the alkyl group is derived from a secondary alcohol (c) a viscosity at 20 ° C. of 2000 mPa · s or more: poly from which an alkyl group is derived from a secondary alcohol Oxyalkylene alkyl ether
  2. 　ＨＬＢ値が１０～１３．５であり、かつアルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテルを含油スカムに添加する、含油スカムの油水分離方法。 An oil-water separation method for oil-impregnated scum, wherein polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 and an alkyl group derived from a secondary alcohol is added to the oil-impregnated scum.
  3. 　含油スカムが、圧延工程で発生した含油スカムである、請求項１又は２に記載の含油スカムの油水分離方法。 The method for oil-water separation of oil-impregnated scum according to claim 1 or 2, wherein the oil-impregnated scum is an oil-impregnated scum generated in a rolling process.
  4. 　ＨＬＢ値が１０～１３．５のポリオキシアルキレンアルキルエーテルを含有してなる、圧延工程で発生した２０℃の粘度が２０００ｍＰａ・ｓ未満の含油スカム用の油水分離剤。 An oil-water separator for oil-impregnated scum having a viscosity at 20 ° C. of less than 2000 mPa · s generated in the rolling process, comprising a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5.
  5. 　アルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテルを含有してなる、圧延工程で発生した２０℃の粘度が１０００ｍＰａ・ｓ以上の含油スカム用の油水分離剤。 An oil / water separator for oil-impregnated scum having a viscosity at 20 ° C. of 1000 mPa · s or more generated in a rolling process, wherein the alkyl group contains a polyoxyalkylene alkyl ether derived from a secondary alcohol.
  6. 　ＨＬＢ値が１０～１３．５であり、かつアルキル基が第二級アルコールに由来するポリオキシアルキレンアルキルエーテルを含有してなる、圧延工程で発生した含油スカム用の油水分離剤。 An oil-water separator for oil-impregnated scum generated in the rolling process, comprising a polyoxyalkylene alkyl ether having an HLB value of 10 to 13.5 and an alkyl group derived from a secondary alcohol.
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