WO2012029824A1 - Ｗ／ｏナノエマルション及びその製造方法 - Google Patents

Ｗ／ｏナノエマルション及びその製造方法 Download PDF

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WO2012029824A1
WO2012029824A1 PCT/JP2011/069698 JP2011069698W WO2012029824A1 WO 2012029824 A1 WO2012029824 A1 WO 2012029824A1 JP 2011069698 W JP2011069698 W JP 2011069698W WO 2012029824 A1 WO2012029824 A1 WO 2012029824A1
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weight
surfactant
parts
emulsion
water
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PCT/JP2011/069698
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English (en)
French (fr)
Japanese (ja)
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藤田　豊久
朝菜 國分
ジョルジ ドドビバ
荒又　幹夫
清水　孝之
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国立大学法人東京大学
サム工業株式会社
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Priority to US13/819,537 priority Critical patent/US20130219772A1/en
Priority to CN2011800415911A priority patent/CN103097500A/zh
Priority to EP11821839.5A priority patent/EP2612898A4/en
Priority to KR1020137005774A priority patent/KR20140029350A/ko
Publication of WO2012029824A1 publication Critical patent/WO2012029824A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/328—Oil emulsions containing water or any other hydrophilic phase

Definitions

  • the present invention relates to a W / O nanoemulsion, a method for producing the same, and a fuel having the W / O nanoemulsion.
  • Emulsion fuel is said to have the effect of suppressing the generation of nitrogen oxides and particulate matter and reducing the environmental burden caused by the gas discharged from the internal combustion engine.
  • low boiling water particles When ignited by an internal combustion engine, low boiling water particles are first vaporized and evaporated, and at that time, the surrounding oil is scattered and becomes particles of finer diameter. These oil particles have a larger area in contact with oxygen per volume, resulting in less local incomplete combustion, increasing combustion efficiency, reducing the amount of particulate matter (Particulate Matter, PM), and simultaneously containing water.
  • the temperature of the internal combustion engine decreases, so that the generation of nitrogen oxides due to the formation reaction of Zeldovic NO can also be suppressed.
  • An increase in combustion efficiency also leads to a decrease in CO and a reduction in CO2.
  • CHIESA M et al . Thermal conductivity and viscosity of water-in-oil nanoemulsions, Colloids Surf A, Vol.326 No.1-2 Page. 67-72 (2008).
  • MAGDASSI S. et al . A new method for preparation of poly-lauryl acrylate nanoparticles from nanoemulsions obtained by the phase inversion temperature process, Polym Adv Technol, Vol.18 No.9 Page. 705-711 (2007).
  • PORRAS M et al . Studies of formation of W / O nano-emulsions, Colloids Surf A, Vol.249 No.1 / 3 Page. 115-118 (2004).
  • an object of the present invention is to solve the above problems. Specifically, an object of the present invention is to provide a W / O type nanoemulsion that exists stably even after long-term storage, for example, storage for 6 months. In addition to the above object, or in addition to the above object, an object of the present invention is to provide a W / O nanoemulsion having a combustion efficiency better than kerosene or light oil, or a fuel having the W / O nanoemulsion. There is to do. Furthermore, the object of the present invention is to provide a W / O nanoemulsion capable of suppressing the amount of NOx and / or CO generated by combustion in addition to the above object or in addition to the above object, or the W / O nanoparticle. It is to provide a fuel having an emulsion.
  • ⁇ 1> a) Water: more than 0% by weight and 30% by weight or less, preferably 5 to 20% by weight; b) Oil: less than 100% by weight, 70% by weight or more, preferably 95-80% by weight; c) at least one nonionic surfactant having an HLB value of 1 to 10, preferably 3 to 8 when standardized with 100 parts by weight of oil: 1 to 30 parts by weight, preferably 10 to 20 parts by weight; and d) When standardized with 100 parts by weight of water, at least one selected from the group consisting of an anionic surfactant, a cationic surfactant and an amphoteric surfactant: 0.1 to 30 parts by weight, preferably 0.8. 5-20 parts by weight; W / O type emulsion having A W / O emulsion in which the 50% average particle diameter of water particles of the W / O emulsion is 100 nm or less.
  • the 50% average particle size of the water particles of the W / O emulsion is 5 to 100 nm, preferably 5 to 50 nm, more preferably 5 to 30 nm, and most preferably 5 to 20 nm. Is good.
  • b) oil is a group consisting of kerosene, gasoline, light oil, heavy oil (including A heavy oil, B heavy oil and C heavy oil), alcohol, biofuel and ethyl tert-butyl ether. And at least one selected from the group consisting of kerosene, light oil, A heavy oil and B heavy oil, more preferably kerosene or light oil.
  • the nonionic surfactant is polyoxyethylene glycol, fatty acid sorbitan ester, alkyl polyglucoside, fatty acid diethanolamide, alkyl monoglyceryl ether, alkyl glycoside, polyethylene At least one selected from the group consisting of glycol and polyvinyl alcohol, preferably at least one selected from the group consisting of polyoxyethylene glycol, fatty acid sorbitan ester, and alkylpolyglucoside, more preferably polyoxyethylene glycol. Is good.
  • d) preferably has an anionic surfactant.
  • d) preferably comprises only an anionic surfactant.
  • the anionic surfactant is a fatty acid salt, a monoalkyl sulfate, an alkyl polyoxyethylene sulfate, an alkyl benzene sulfonate, a monoalkyl phosphate, and At least one selected from the group consisting of sulfosuccinic acid type surfactants (ethyl hexyl sulfosuccinate, etc.), preferably consisting of fatty acid salts, monoalkyl sulfates, alkyl polyoxyethylene sulfates, and alkylbenzene sulfonates. It may be at least one selected from the group, more preferably a monoalkyl sulfate.
  • d) preferably has a cationic surfactant.
  • d) preferably comprises only a cationic surfactant.
  • the cationic surfactant is an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, and an alkylbenzyldimethylammonium salt And at least one selected from the group consisting of alkyltrimethylammonium salts.
  • d) preferably has an amphoteric surfactant.
  • d) preferably comprises only an amphoteric surfactant.
  • the amphoteric surfactant is composed of alkyldimethylamine oxide and alkylcarboxybetaine. It is good that it is at least one selected from the group.
  • ⁇ 14> A fuel having the W / O emulsion according to any one of ⁇ 1> to ⁇ 13>.
  • ⁇ 15> A fuel comprising only the W / O emulsion according to any one of the above items ⁇ 1> to ⁇ 13>.
  • ⁇ 16> A fuel consisting essentially only of the W / O emulsion according to any one of the above items ⁇ 1> to ⁇ 13>.
  • ⁇ 16> a) Water: more than 0% by weight and 30% by weight or less, preferably 5 to 20% by weight; b) Oil: less than 100% by weight, 70% by weight or more, preferably 95-80% by weight; c) at least one nonionic surfactant having an HLB value of 1 to 10, preferably 3 to 8 when standardized with 100 parts by weight of oil: 1 to 30 parts by weight, preferably 10 to 20 parts by weight; and d) When standardized with 100 parts by weight of water, at least one selected from the group consisting of an anionic surfactant, a cationic surfactant and an amphoteric surfactant: 0.1 to 30 parts by weight, preferably 0.8.
  • W / O type emulsion having W / O type in which the 50% average particle size of water particles of the W / O type emulsion is 100 nm or less, preferably 5 to 100 nm, preferably 5 to 50 nm, more preferably 5 to 30 nm, and most preferably 5 to 20 nm.
  • An emulsion manufacturing method comprising: i) a) preparing water; ii) b) preparing oil; iii) c) providing a nonionic surfactant; iv) preparing a surfactant of d); and v) mixing a) to d); The said method of obtaining the said W / O type
  • step 3 In the v) mixing step of ⁇ 16> above, v-1) mixing ii) step oil; and iii) step nonionic surfactant; Separately, v-2) i) step water; and iv) step surfactant is mixed, v-3) It is preferable to have a step of mixing the mixture obtained in step v-1) with the mixture obtained in step v-2).
  • oil is a group consisting of kerosene, gasoline, light oil, heavy oil (including A heavy oil, B heavy oil and C heavy oil), alcohol, biofuel and ethyl tert-butyl ether. And at least one selected from the group consisting of kerosene, light oil, A heavy oil and B heavy oil, more preferably kerosene or light oil.
  • the nonionic surfactant is polyoxyethylene glycol, fatty acid sorbitan ester, alkyl polyglucoside, fatty acid diethanolamide, alkyl monoglyceryl ether, alkyl glycoside, polyethylene At least one selected from the group consisting of glycol and polyvinyl alcohol, preferably at least one selected from the group consisting of polyoxyethylene glycol, fatty acid sorbitan ester, and alkylpolyglucoside, more preferably polyoxyethylene glycol. Is good.
  • d) preferably has an anionic surfactant.
  • d) preferably comprises only an anionic surfactant.
  • the anionic surfactant is a fatty acid salt, a monoalkyl sulfate, an alkyl polyoxyethylene sulfate, an alkyl benzene sulfonate, a monoalkyl phosphate, and At least one selected from the group consisting of sulfosuccinic acid type surfactants (ethyl hexyl sulfosuccinate, etc.), preferably consisting of fatty acid salts, monoalkyl sulfates, alkyl polyoxyethylene sulfates, and alkylbenzene sulfonates. It may be at least one selected from the group, more preferably a monoalkyl sulfate.
  • d) preferably has a cationic surfactant.
  • d) preferably comprises only a cationic surfactant.
  • the cationic surfactant is an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, and an alkylbenzyldimethylammonium salt And at least one selected from the group consisting of alkyltrimethylammonium salts.
  • d preferably has an amphoteric surfactant.
  • ⁇ 27> In any one of the above items ⁇ 16> to ⁇ 19>, d) preferably comprises only an amphoteric surfactant.
  • the amphoteric surfactant is composed of alkyldimethylamine oxide and alkylcarboxybetaine. It is good that it is at least one selected from the group.
  • the present invention it is possible to provide a W / O nanoemulsion that exists stably even after long-term storage, for example, 6 months storage.
  • the present invention provides a W / O nanoemulsion having a combustion efficiency better than kerosene or light oil, or a fuel having the W / O nanoemulsion. Can do.
  • a W / O type nanoemulsion capable of suppressing the amount of NOx and / or CO generated by combustion, or the W / O type nanoemulsion, The fuel which has can be provided.
  • FIG. It is a figure which shows typically the W / O type
  • FIG. It is a figure which shows the result of the ignition combustion test of the comparative example 1 (only kerosene). It is a figure which shows the result of the ignition combustion test of the comparative example 2 (combination of nonionic surfactant). It is a figure which shows the anionic surfactant amount dependence of the average particle diameter of the W / O type
  • the present application provides a “W / O type emulsion”, a fuel having the “W / O type emulsion”, a method for producing the “W / O type emulsion”, and the like. Hereinafter, it demonstrates in order.
  • the present application provides a W / O emulsion in which the 50% average particle size of water particles of the W / O emulsion is 100 nm or less.
  • “50% average particle diameter” refers to the median diameter at which the cumulative distribution is 0.5.
  • “50% average particle diameter of water particles of W / O type emulsion” means the following. That is, the W / O type emulsion of the present application has a structure as shown in FIG. As an example, FIG.
  • FIG. 1 shows that the W / O type emulsion of the present application is mixed with water and a nonionic surfactant to form a microemulsion, and then an anionic surfactant is further mixed to form a nanoemulsion.
  • the nanoemulsion in FIG. 1 has water particles at the center, and hydrocarbon chains are arranged on the outer periphery thereof. Therefore, the “water particles of the W / O type emulsion” are water particles arranged at the center of the nanoemulsion in FIG. Therefore, “50% average particle diameter of water particles of W / O type emulsion” is explained as an example in FIG. 1. A median having a cumulative distribution of 0.5 with respect to water particles arranged at the center of the nanoemulsion. The diameter.
  • the W / O emulsion of the present invention comprises: a) water; b) oil; c) a nonionic surfactant having an HLB value of 1 to 10, preferably 3 to 8; and d) an anionic surfactant, a cation. Or at least one selected from the group consisting of surfactants and amphoteric surfactants, or substantially consists only of a) to d), or consists only of a) to d).
  • a nonionic surfactant having an HLB value of 1 to 10, preferably 3 to 8 means that when only one kind of nonionic surfactant is used, the HLB value of the nonionic surfactant used only in the one kind falls within the above range. It means that there is.
  • the HLB value is defined as in the following formula (1).
  • the whole HLB t value of 2 or more types of nonionic surfactants to be used is calculated
  • W i represents the weight of the i-th nonionic surfactant
  • HLB i represents the HLB value of the i-th nonionic surfactant.
  • this HLB t value is used as the HLB value.
  • nonionic surfactant A when 2 types (nonionic surfactant A; and nonionic surfactant B) are used as a nonionic surfactant, the whole HLB t value becomes like Formula (3) from Formula (2). .
  • a) to d) should have the following blending ratios.
  • the oil is at least one selected from the group consisting of kerosene, gasoline, light oil, heavy oil (including heavy oil A, heavy oil B and heavy oil C), alcohol, biofuel and ethyl tert-butyl ether, preferably kerosene, light oil, At least one selected from the group consisting of A heavy oil and B heavy oil, more preferably kerosene or light oil.
  • Nonionic surfactant is at least one selected from the group consisting of polyoxyethylene glycol, fatty acid sorbitan ester, alkyl polyglucoside, fatty acid diethanolamide, alkyl monoglyceryl ether, alkyl glycoside, polyethylene glycol, and polyvinyl alcohol, preferably Is at least one selected from the group consisting of polyoxyethylene glycol, fatty acid sorbitan ester, and alkyl polyglucoside, more preferably polyoxyethylene glycol.
  • the D) has an anionic surfactant as one aspect
  • the anionic surfactant is a fatty acid salt (for example, sodium linoleate, sodium oleate), a monoalkyl sulfate (for example, sodium dodecyl sulfonate), an alkyl polyoxyethylene sulfate (for example, polyoxyethylene lauryl).
  • alkylbenzene sulfonates eg, sodium dodecylbenzene sulfonate
  • monoalkyl phosphates eg, sodium polyoxyethylene alkyl ether phosphate
  • sulfosuccinic acid type surfactants ethyl hexyl sulfosuccinate
  • acid salts etc., preferably fatty acid salts (for example, sodium linoleate, preferably sodium oleate), monoalkyl sulfates, alkylpolyoxyethylene sulfates, and a At least one selected from the group consisting of kill benzenesulfonate, and more preferably, a monoalkyl sulfate.
  • the salt include sodium salt, ammonium salt, potassium salt and the like, preferably sodium salt or ammonium salt, more preferably sodium salt.
  • d) may have a cationic surfactant or consist only of a cationic surfactant.
  • the cationic surfactant is an alkyltrimethylammonium salt (for example, C 12 H 25 -N + (CH 3 ) 3 ⁇ Cl ⁇ or the like), a dialkyldimethylammonium salt (for example, C 12 H 25 -N + ( C 8 H 17) (CH 3 ) 2 ⁇ Cl - , etc.), and alkyl benzyl dimethyl ammonium salts (e.g., at least one selected from the group consisting of decyl isononyl dimethyl ammonium salts), preferably an alkyl trimethyl ammonium salt (e.g. , C 12 H 25 —N + (CH 3 ) 3 ⁇ Cl ⁇ ).
  • d) preferably has an amphoteric surfactant or consists only of an amphoteric surfactant.
  • the amphoteric surfactants are alkyl dimethylamine oxide (such as C 12 H 25 — (CH 3 ) 2 NO) and alkyl carboxybetaine (such as C 12 H 25 — (CH 3 ) 2 N + CH 2 COO - may be at least one selected from the group consisting of a).
  • the present application provides i) a fuel having the W / O emulsion; ii) a fuel consisting only of the W / O emulsion; or iii) a fuel consisting essentially of the W / O emulsion.
  • alcohol for example, methanol, ethanol, etc.
  • the component which may be contained other than a W / O type emulsion is not limited to these.
  • the W / O type emulsion of the present application can be produced, for example, by the following method. That is, i) a) preparing water; ii) b) preparing oil; iii) c) providing a nonionic surfactant; iv) preparing a surfactant of d); and v) mixing a) to d);
  • a) water; b) oil; c) nonionic surfactant; and d) surfactant have the same definition as described above.
  • a mechanical emulsification method, a phase transition method, a phase inversion emulsification method, a D phase emulsification method, a gel emulsification method, and the like can be used, but are not limited thereto.
  • a homogenizer of a mechanical emulsification method it is preferable to use a homogenizer of a mechanical emulsification method, a counter collision machine, a screw type, an ultrasonic type, or the like.
  • the mixing step includes a method of sequentially mixing a) to d) prepared in i) to iv) described above, or a method of mixing them together, and in either case, the emulsion of the present application can be obtained. Can do.
  • it is a technique of mixing sequentially, v-1) mixing ii) step oil; and iii) step nonionic surfactant; Separately, v-2) i) step water; and iv) step surfactant is mixed, v-3)
  • the v-1) step, v-2) step, and v-3) step can all use conventional mixing techniques.
  • Nonionic surfactant DSK NL-15 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene lauryl) was added to a liquid of 850 g of kerosene (85 wt% of kerosene when the total of 150 g of water and 850 g of kerosene described below is 100 wt%).
  • nonionic surfactant DSK NL-50 (Daiichi Kogyo Seiyaku) 34 g 4 parts by weight when kerosene is standardized as 100 parts by weight was added and stirred to mix to make liquid A.
  • the whole HLB value of the nonionic surfactant in A liquid was 6.12 by the said Formula (2).
  • liquid A Separately from the liquid A, 150 g of water (when the total of 150 g of water and 850 g of kerosene is 100% by weight, 15% by weight of water) and 15 g of anionic surfactant, sodium dodecyl sulfate (manufactured by Nacalai) When standardized as 100 parts by weight, 10 parts by weight) was added, stirred and mixed to obtain Liquid B. When this A liquid and B liquid were stirred for 5 minutes with the homogenizer (PH91 by SMT Company), the colorless and transparent liquid, ie, W / O nanoemulsion, was obtained.
  • anionic surfactant sodium dodecyl sulfate
  • Liquid A and liquid B were mixed at the same mixing ratio as in Example 1 except that an opposing collision machine (manufactured by Environmental Innovation Industry Co., Ltd.) was used instead of the homogenizer (PH91 manufactured by SMT Company) used in Example 1.
  • the obtained W / O nanoemulsion was measured by an ignition flammability test (fuel ignition flammability test apparatus FIA-100 manufactured by Fuel Tech Japan Co., Ltd.).
  • the results are shown in Table 1 and FIG. In the upper graph of FIG. 2, it shows that the fuel ignition combustion test was done 10 times.
  • the horizontal axis represents time (ms)
  • the vertical axis represents pressure (bar), the pressure after start and combustion, and an average value thereof.
  • FIG. 2 In the lower graph of FIG. 2, the horizontal axis indicates time (ms), the vertical axis indicates pressure / time (bar / ms), and the upper graph of FIG. 2 is time-differentiated so that combustion efficiency can be compared.
  • a blender HBB type manufactured by Yamato Scientific Co., Ltd.
  • Tables 1 to 3 and FIGS. 2 to 4 show that the W / O nanoemulsion of Example 2 ignites faster than kerosene alone (kerosene only: 10.95 ms; W / O of Example 2). Type nanoemulsion: 7.75 ms).
  • MCP main combustion period
  • W / O type nanoemulsion 5.23 ms.
  • the W / O type nanoemulsion of Example 2 is higher than kerosene (kerosene only: 41; W / O type nanoemulsion of Example 2: 48.5). From these, it can be seen that the W / O nanoemulsion of Example 2 has good combustion characteristics.
  • Nonionic surfactant DSK NL-15 (same as above) 144 g (standardized with 100 parts by weight of kerosene) in a solution of 900 g of kerosene (90% by weight of kerosene when the total of 100 g of water and 900 g of kerosene described below is 100% by weight) 16 parts by weight) and 36 g of nonionic surfactant DSK NL-50 (same as above) (4 parts by weight when kerosene is standardized as 100 parts by weight) were added and stirred to obtain a solution A.
  • the whole HLB value of the nonionic surfactant in A liquid was 6.12 by the said Formula (2).
  • liquid A Separately from the liquid A, 10 g of an anionic surfactant and sodium dodecyl sulfate (manufactured by Nacalai Co., Ltd.) are added to 100 g of water (when the total of 100 g of water and 900 g of kerosene is 100% by weight, 10% by weight of water). When standardized as 100 parts by weight, 10 parts by weight) was added, stirred and mixed to obtain Liquid B. Liquid A and liquid B were mixed in the same manner as in Example 1 to obtain a colorless and transparent liquid, that is, a W / O nanoemulsion.
  • an anionic surfactant and sodium dodecyl sulfate manufactured by Nacalai Co., Ltd.
  • Example 2 when the particle size distribution of the W / O nanoemulsion was measured by the laser light scattering method, the 50% average particle size of the water particles was about 10 nm. With respect to the stability, when observed by the same method as in Example 1, no separation occurred. Moreover, even if it left still at normal temperature for 1 year, it was a transparent state.
  • Nonionic surfactant DSK NL-15 128 g (100 parts by weight of kerosene) standardized in 800 g of kerosene (80% by weight of kerosene when the total of 200 g of water and 800 g of kerosene described below is 100% by weight) 16 parts by weight) and 32 g of nonionic surfactant DSK NL-50 (same as above) (4 parts by weight when kerosene was standardized as 100 parts by weight) were added and stirred to prepare a solution A.
  • the whole HLB value of the nonionic surfactant in A liquid was 6.12 by the said Formula (2).
  • liquid A Separately from the liquid A, 20 g of anionic surfactant, sodium dodecyl sulfate (manufactured by Nacalai Co., Ltd.), 20 g of water (200 wt.% When the total of 200 g of water and 800 g of kerosene is 100 wt.%) When standardized as 100 parts by weight, 10 parts by weight) was added, stirred and mixed to obtain Liquid B. Liquid A and liquid B were mixed in the same manner as in Example 1 to obtain a colorless and transparent liquid, that is, a W / O nanoemulsion.
  • Example 2 when the particle size distribution of the W / O nanoemulsion was measured by the laser light scattering method, the 50% average particle size of the water particles was about 10 nm. With respect to the stability, when observed by the same method as in Example 1, no separation occurred. Moreover, even if it left still at normal temperature for 1 year, it was a transparent state.
  • Example 1 The anionic surface activity used in Example 1, in place of sodium dodecyl sulfate, dioctyl sulfosuccinate (Aerosol 0T manufactured by Wako Pure Chemical Industries, Ltd.) was used, and the same mixing ratio as in Example 1 was carried out.
  • a colorless and transparent liquid, W / O nanoemulsion was prepared using the method of mixing liquid A and liquid B as in Example 1.
  • the 50% average particle size of the water particles was about 10 nm. With respect to the stability, when observed by the same method as in Example 1, no separation occurred.
  • Example 7 A liquid A was prepared in the same manner as in Example 1.
  • the amount of sodium dodecyl sulfate in the liquid B of Example 1 was changed to 0.75 g (0.5 parts by weight when water was standardized as 100 parts by weight) instead of 15 g (Example 7), 4.2 g ( Except for 2.8 parts by weight when standardized as 100 parts by weight of water (Example 8) and 7.5 g (5 parts by weight when standardized as 100 parts by weight of water) (Example 9)
  • Liquid B was prepared in the same manner as in Example 1, and liquid A and liquid B were mixed in the same manner as in Example 1 to obtain a colorless and transparent liquid, W / O nanoemulsion.
  • Example 1 When the particle size distribution of the obtained W / O nanoemulsion was measured by a laser light scattering method in the same manner as in Example 1, the result of FIG. 5 was obtained (the amount of ionic surfactant: 10 wt% was carried out). Results of Example 1). From FIG. 5, in the formulations of Example 1 and Examples 7 to 9, the average particle size of the emulsion increases when the amount of the anionic surfactant is small, and the average of the emulsion increases when the amount of the anionic surfactant is large. A trend towards smaller particle size was observed.
  • Example 10 (Example 10) In Example 1, instead of the nonionic surfactant DSK NL-50, a nonionic surfactant DSK NL-40 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene lauryl ether, HLB: 9.5) was used. In the same manner as in Example 1, a colorless and transparent liquid, that is, a W / O nanoemulsion was obtained. In addition, the whole HLB value of the nonionic surfactant in A liquid was 5.9 by the said Formula (2). When the particle size distribution of the obtained W / O nanoemulsion was measured by the same method as in Example 1, the 50% average particle size of the water particles was about 10 nm. With respect to the stability, when observed by the same method as in Example 1, no separation occurred.
  • Example 11 In Example 10, a colorless and transparent liquid was obtained in the same manner as in Example 1 except that an anionic surfactant and sodium oleate (manufactured by Nacalai) were used instead of the anionic surfactant and sodium dodecyl sulfate. That is, a W / O nanoemulsion was obtained.
  • the HLB value of the whole nonionic surfactant in A liquid was 5.9 similarly to Example 10.
  • the particle size distribution of the obtained W / O nanoemulsion was measured by the same method as in Example 1, the 50% average particle size of the water particles was about 50 nm. With respect to the stability, when observed by the same method as in Example 1, no separation occurred.
  • Example 12 In Example 3, except that the amount of sodium dodecyl sulfate was changed from 10 g to 20 g (20 parts by weight when water was standardized to 100 parts by weight), a colorless transparent liquid, ie, A W / O nanoemulsion was obtained.
  • the particle size distribution of the obtained W / O nanoemulsion was measured by the same method as in Example 1, the 50% average particle size of the water particles was about 8 nm. With respect to the stability, when observed by the same method as in Example 1, no separation occurred.
  • Example 13 In Example 4, except that the amount of sodium dodecyl sulfate was changed from 20 g to 40 g (20 parts by weight when water was standardized to 100 parts by weight), a colorless and transparent liquid, ie, A W / O nanoemulsion was obtained.
  • the particle size distribution of the obtained W / O nanoemulsion was measured by the same method as in Example 1, the 50% average particle size of the water particles was about 20 nm. With respect to the stability, when observed by the same method as in Example 1, no separation occurred.
  • Nonionic surfactant DSK NL-15 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene lauryl is added to a liquid of 850 g of gasoline (when the total of 150 g of water and 850 g of gasoline described below is 100% by weight, gasoline 85% by weight).
  • the whole HLB value of the nonionic surfactant in A liquid was 6.12 from the said Formula (2).
  • 150 g of water (15 wt% of water when the total of 150 g of water and 850 g of gasoline is 100 wt%)
  • 15 g of anionic surfactant, sodium dodecyl sulfate (manufactured by Nacalai)
  • Liquid B Liquid B
  • the particle size distribution of the obtained W / O nanoemulsion could not be measured by the same method as in Example 1 because the permeability was large. However, since the obtained W / O emulsion is colorless and transparent and phase separation does not occur, the 50% average particle diameter of water particles is estimated to be 100 nm or less. With respect to the stability, when observed by the same method as in Example 1, no separation occurred. Moreover, even if it left still at normal temperature for one month, it was in the transparent state.
  • Nonionic surfactant DSK NL-15 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene lauryl is added to a liquid of 850 g of gasoline (when the total of 150 g of water and 850 g of gasoline described below is 100% by weight, gasoline 85% by weight).
  • liquid A Separately from the liquid A, 150 g of water (when the total of 150 g of water and 850 g of gasoline is 100% by weight, 15% by weight of water), anionic surfactant, 10 g of sodium dodecyl sulfate (manufactured by Nacalai), 15 g and 30 g (7 parts by weight, 10 parts by weight, and 20 parts by weight, respectively, when water was standardized at 100 parts by weight) was added and stirred to obtain a liquid B. When this A liquid and B liquid were stirred for 5 minutes with the homogenizer (PH91 by SMT Company), each colorless and transparent liquid, ie, W / O nanoemulsion, was obtained.
  • anionic surfactant 10 g of sodium dodecyl sulfate (manufactured by Nacalai)
  • 15 g and 30 g 7 parts by weight, 10 parts by weight, and 20 parts by weight, respectively, when water was standardized at 100 parts by weight
  • the particle size distribution of the obtained W / O nanoemulsion could not be measured by the same method as in Example 1 because the permeability was large. However, since the obtained W / O emulsion is colorless and transparent and phase separation does not occur, the 50% average particle diameter of water particles is estimated to be 100 nm or less. With respect to the stability, when observed by the same method as in Example 1, no separation occurred. Moreover, even if it left still at normal temperature for one month, it was in the transparent state.
  • Nonionic surfactant DSK NL-15 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene lauryl) was added to a liquid of 850 g of light oil (85% by weight of light oil when the total of 150 g of water and 850 g of light oil described later is 100% by weight).
  • the whole HLB value of the nonionic surfactant in A liquid was 6.12 from the said Formula (2).
  • 150 g of water (15% by weight when the total of 150 g of water and 850 g of light oil is 100% by weight
  • 15 g of anionic surfactant, sodium dodecyl sulfate (manufactured by Nacalai)
  • Liquid B Liquid B
  • the 50% average particle size of the water particles was about 10 nm.
  • the stability when observed by the same method as in Example 1, no separation occurred. Moreover, even if it left still at normal temperature for one month, it was in the transparent state.
  • Nonionic surfactant DSK NL-15 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene lauryl) was added to a liquid of 850 g of light oil (85% by weight of light oil when the total of 150 g of water and 850 g of light oil described later is 100% by weight).
  • liquid A Separately from the liquid A, 150 g of water (when the total of water 150 g and light oil 850 g is 100 wt%, water 15 wt%), anionic surfactant, sodium dodecyl sulfate (manufactured by Nacalai) 2.5 g and 7.5 g (1.7 parts by weight and 5 parts by weight, respectively when water is standardized to 100 parts by weight) was added, stirred and mixed to obtain a liquid B. When this A liquid and B liquid were stirred for 5 minutes with the homogenizer (PH91 by SMT Company), the colorless and transparent liquid, ie, W / O nanoemulsion, was obtained.
  • anionic surfactant sodium dodecyl sulfate
  • sodium dodecyl sulfate manufactured by Nacalai
  • the 50% average particle size of the water particles was about 10 nm, respectively.
  • the stability when observed by the same method as in Example 1, no separation occurred. Moreover, even if it left still at normal temperature for one month, it was in the transparent state.
  • Example 18 A colorless and transparent liquid, that is, a W / O nanoemulsion, was obtained in the same manner as in Example 17, except that “Heavy oil A” was used instead of “light oil” in Example 17.
  • the particle size distribution of the obtained W / O nanoemulsion was measured by the same method as in Example 1, the 50% average particle size of the water particles was about 10 nm, respectively.
  • the stability when observed by the same method as in Example 1, no separation occurred. Moreover, even if it left still at normal temperature for one month, it was in the transparent state.
  • Nonionic surfactant DSK NL-15 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyacrylic acid) was added to a liquid of 850 g of C heavy oil (85% by weight of C heavy oil when the total of 150 g of water described below and 850 g of C heavy oil was 100% by weight).
  • the obtained W / O emulsion was colorless and transparent, and it was observed by the same method as in Example 1 regarding the stability. As a result, no phase separation occurred, so the 50% average particle size of the water particles was 100 nm. It is estimated that Moreover, even if it left still at normal temperature for one month, it was in the transparent state.
  • Nonionic surfactant DSK NL-15 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxygen) was added to a liquid of 850 g of C heavy oil (85% by weight of gasoline when the total of 150 g of water and 850 g of C heavy oil described later was 100% by weight).
  • anionic surfactant sodium dodecyl sulfate (manufactured by Nacalai Co., Ltd.) 2.5 g is added to 150 g of water (when the total of 150 g of water and 850 g of C heavy oil is 100 wt%) 10 g and 15 g (1.7 parts by weight, 6.7 parts by weight and 10 parts by weight, respectively, when water is standardized at 100 parts by weight) were added, stirred and mixed to obtain Liquid B.
  • this A liquid and B liquid were stirred for 5 minutes with the homogenizer (PH91 by SMT Company), the colorless and transparent liquid, ie, W / O nanoemulsion, was obtained.
  • the particle size distribution of the obtained W / O nanoemulsion could not be measured by the same method as in Example 1 because the permeability was small.
  • the obtained W / O emulsion was colorless and transparent, and it was observed by the same method as in Example 1 regarding the stability. As a result, no phase separation occurred, so the 50% average particle size of the water particles was 100 nm. It is estimated that Moreover, even if it left still at normal temperature for one month, it was in the transparent state.
  • Nonionic surfactant DSK NL-15 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene lauryl) was added to a liquid of 850 g of kerosene (85 wt% of kerosene when the total of 150 g of water and 850 g of kerosene described below is 100 wt%).
  • nonionic surfactant DSK NL-50 (Daiichi Kogyo Seiyaku) 34 g 4 parts by weight when kerosene is standardized as 100 parts by weight was added and stirred to mix to make liquid A.
  • the whole HLB value of the nonionic surfactant in A liquid was 6.12 by the said Formula (2).
  • solution B Separately from the liquid A, 150 g of water (15% by weight of water when the total of 150 g of water and 850 g of kerosene is 100% by weight), 15 g of anionic surfactant, sodium oleate (manufactured by Nacalai) When standardized as 100 parts by weight, 10 parts by weight) was added and stirred and mixed. Next, when an aqueous solution of sodium oleate was placed in a DC electric field through a cation exchange membrane, an alkaline aqueous solution containing oleate ions on the anode side was obtained, which was designated as solution B.
  • the obtained liquid B was free of sulfur S and had an aqueous solution with less Na ions as compared with an aqueous sodium dodecyl sulfate solution.
  • the homogenizer PH91 by SMT Company
  • the colorless and transparent liquid ie, W / O nanoemulsion
  • the 50% average particle size of the water particles was about 10 nm.
  • the stability when observed by the same method as in Example 1, no separation occurred. Moreover, even if it left still at normal temperature for one month, it was in the transparent state.

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PCT/JP2011/069698 2010-08-31 2011-08-31 Ｗ／ｏナノエマルション及びその製造方法 WO2012029824A1 (ja)

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US13/819,537 US20130219772A1 (en) 2010-08-31 2011-08-31 W/o nanoemulsion and method for producing same
CN2011800415911A CN103097500A (zh) 2010-08-31 2011-08-31 W/o纳米乳液及其制造方法
EP11821839.5A EP2612898A4 (en) 2010-08-31 2011-08-31 WATER-IN-OIL NANOEMULSION AND METHOD FOR THE PRODUCTION THEREOF
KR1020137005774A KR20140029350A (ko) 2010-08-31 2011-08-31 Ｗ／ｏ 나노에멀젼 및 그 제조방법

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JP5987779B2 (ja) * 2013-05-01 2016-09-07 信越化学工業株式会社 希土類酸化物粉末の製造方法
CN104130760B (zh) * 2014-07-04 2017-09-15 中国石油天然气股份有限公司 一种堵水用高凝稠油活化剂及油井堵水方法
EP3218452B1 (en) 2014-11-10 2019-07-31 EME Finance Ltd Water in diesel oil fuel micro-emulsions.
WO2016074903A1 (en) 2014-11-10 2016-05-19 Eme International Limited Device for mixing water and diesel oil, apparatus and process for producing a water/diesel oil micro-emulsion.
CN104962261B (zh) * 2015-05-21 2017-11-10 中国石油天然气股份有限公司 一种堵水用稠化剂以及由其制成的堵水用稀油稠化剂
CN105331396A (zh) * 2015-11-03 2016-02-17 谭人凤 节能减排纳米油制造系统与方法
KR102022679B1 (ko) * 2016-04-21 2019-09-18 한양대학교 에리카산학협력단 디젤 엔진용 연료 조성물
IT201600132801A1 (it) 2016-12-30 2018-06-30 Eme International Ltd Apparato e processo per produrre liquido derivante da biomassa, biocarburante e biomateriale
US11542451B2 (en) * 2017-08-18 2023-01-03 Fuel Technology, LLC Water in fuel nanoemulsion and method of making the same
WO2022096310A1 (en) * 2020-11-04 2022-05-12 Basf Se Aqueous emulsifier package with anionic surfactant for fuel emulsion
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