JP2007119627A - Flammable liquid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flammable liquid contributing to the global environment, industry or the like of next generation. <P>SOLUTION: The flammable liquid is obtained by allowing a flammable liquid to contain a metal porphyrin complex, and can reduce the amount of carbon dioxide. As a result, the discharged amount of the carbon dioxide caused in general use of the flammable liquid, e.g. the combustion in an automobile, thermal power generation and the like can be reduced. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a flammable liquid.

  In recent years, problems that will contribute to the future of humankind, such as global environmental problems, have been seriously discussed and researched and reported at an international level as international problems. For example, examples of problems that will contribute to the future of humankind include the depletion of resources such as petroleum, the problem of global warming due to the emission of carbon dioxide, the impact on the human health due to environmental hormones, and the ultraviolet rays caused by the destruction of the ozone layer. The influence of. There is no need to prove how serious these are.

  Liquid organic solvents, crude oil-based products, petroleum products, petrochemical raw materials, liquefied natural gas, gasoline, oil products, liquids including volatile oils, cutting oils, and machine oils (including mixed liquids with non-flammable liquids) ), And these combustible liquids such as waste oil are burned to obtain electric energy and mechanical energy from heat energy or heat energy, and waste oil is incinerated by combustion.

  However, flammable liquids release carbon dioxide by a chemical reaction between carbon and oxygen by incineration or the like. Carbon dioxide emissions, for example, according to the Kyoto Protocol (the protocol adopted at the 3rd Conference of the Parties (COP3) held in Kyoto in December 1997 to achieve the objectives of the Framework Convention on Climate Change) In Japan, a 6% reduction is urgently needed. Therefore, there is a need for a method of reducing carbon dioxide that is as large as possible.

  This invention is made | formed in view of solving the said subject, and makes it the main objective to provide the combustible liquid which can reduce a carbon dioxide emission more.

  The present invention is characterized in that it is a flammable liquid containing at least a metalloporphyrin complex.

  In the combustible liquid, the metal porphyrin complex is preferably contained in a granular material having a particle size of 50 to 800 nm.

  It is preferable that the flammable liquid is a capsule composed of a nuclear material and an outer shell material including the flammable liquid, and the metal porphyrin complex is contained in the nuclear material.

  The flammable liquid, wherein the shell material is a flammable liquid affinity material having an affinity with the flammable liquid rather than the nuclear material, and a nucleus having an affinity with the nuclear material than the flammable liquid. An affinity substance containing a substance affinity substance is preferred.

  The combustible liquid is preferably dispersed in the metal porphyrin contained in liposomes.

  A flammable liquid that can further reduce carbon dioxide emissions can be provided.

  Hereinafter, the combustible liquid according to the present embodiment, the method for producing the combustible liquid, and the use of the combustible liquid will be described. In addition, this embodiment is only one form for implementing this invention, and this invention is not limited by this embodiment.

"Flammable liquid"
The inventor has studied metal porphyrin complexes that have been conventionally used as oxygen sensors and fuel cell catalysts. As a result of intensive studies, it was possible to obtain an effect of reducing carbon dioxide by including a metal porphyrin complex at the time of carbon dioxide generation. Therefore, by providing a combustible liquid containing at least a metalloporphyrin complex based on this, the amount of carbon dioxide emission is reduced.

  How the metal porphyrin complex contributed to the method of reducing carbon dioxide is because the reaction speed of the metal porphyrin complex is equal to or higher than that during the chemical reaction of carbon and oxygen with the metal porphyrin complex (when generating carbon dioxide). There are large reasons why the reaction between oxygen and carbon is hindered and that the metal porphyrin complex reduces and decomposes carbon dioxide once generated. Therefore, a redox polymer showing the same action may be applied. Hereinafter, a redox polymer may be used in place of the metal porphyrin complex. Examples of the flammable liquid include metal porphyrin complexes and redox polymers. These are not particularly limited as long as carbon dioxide is reduced by inhibiting the binding of carbon and oxygen, or by reducing the generated carbon dioxide and decomposing it into carbon and oxygen.

  The metalloporphyrin complex can be selected from those represented by the following chemical formulas (I) and (II).

（式中、Ｍは、鉄、マンガン、モリブデン、銅、コバルト、クロム、イリジウムから選ばれる金属を示し、４つのＲのうち少なくとも１つは、チオフリル基、ピロリル基、フリル基、メルカプトフェニル基、アミノフェニル基、ヒドロキシフェニル基から選ばれるいずれかの基であり、他のＲは、前記のいずれかの基またはアルキル基、アリール（ａｒｙｌ）基もしくは水素を示す）

(In the formula, M represents a metal selected from iron, manganese, molybdenum, copper, cobalt, chromium, iridium, and at least one of four Rs is a thiofuryl group, a pyrrolyl group, a furyl group, a mercaptophenyl group, Any group selected from an aminophenyl group and a hydroxyphenyl group, and the other R represents any one of the above groups, an alkyl group, an aryl group or hydrogen)

金属ポルフィリン錯体を形成するポルフィリン化合物は特に限られることなく、適宜選択して用いることができるが、例えば、５，１０，１５，２０−テトラキス（２−チオフリル）ポルフィリン、５，１０，１５，２０−テトラキス（３−チオフリル）ポルフィリン、５，１０，１５，２０−テトラキス（２−ピロリル）ポルフィリン、５，１０，１５，２０−テトラキス（３−ピロリル）ポルフィリン、５，１０，１５，２０−テトラキス（２−フリル）ポルフィリン、５，１０，１５，２０−テトラキス（３−フリル）ポルフィリン、５，１０，１５，２０−テトラキス（２−メルカプトフェニル）ポルフィリン、５，１０，１５，２０−テトラキス（３−メルカプトフェニル）ポルフィリン、５，１０，１５，２０−テトラキス（４−メルカプトフェニル）ポルフィリン、５，１０，１５，２０−テトラキス（２−アミノフェニル）ポルフィリン、５，１０，１５，２０−テトラキス（３−アミノフェニル）ポルフィリン、５，１０，１５，２０−テトラキス（４−アミノフェニル）ポルフィリン、５，１０，１５，２０−テトラキス（２−ヒドロキシフェニル）ポルフィリン、５，１０，１５，２０−テトラキス（３−ヒドロキシフェニル）ポルフィリン、５，１０，１５，２０−テトラキス（４−ヒドロキシフェニル）ポルフィリン、［５，１０，１５−トリス（２−チオフリル）−２０−モノ（フェニル）］ポルフィリン、［５，１０，１５−トリス（３−チオフリル）−２０−モノ（フェニル）］ポルフィリン、［５，１０−ビス（２−チオフリル）−１５，２０−ジ（フェニル）］ポルフィリン、［５，１０−ビス（３−チオフリル）−１５，２０−ジ（フェニル）］ポルフィリン、［５，１５−ビス（２−チオフリル）−１５，２０−ジ（フェニル）］ポルフィリン、［５，１５−ビス（３−チオフリル）−１５，２０−ジ（フェニル）］ポルフィリン、［５−モノ（２−チオフリル）−１０，１５，２０−トリ（フェニル）］ポルフィリン、［５−モノ（３−チオフリル）−１０，１５，２０−トリ（フェニル）］ポルフィリンなどを好適例として挙げることができる。

The porphyrin compound forming the metal porphyrin complex is not particularly limited and can be appropriately selected and used. For example, 5,10,15,20-tetrakis (2-thiofuryl) porphyrin, 5,10,15,20 Tetrakis (3-thiofuryl) porphyrin, 5,10,15,20-tetrakis (2-pyrrolyl) porphyrin, 5,10,15,20-tetrakis (3-pyrrolyl) porphyrin, 5,10,15,20-tetrakis (2-furyl) porphyrin, 5,10,15,20-tetrakis (3-furyl) porphyrin, 5,10,15,20-tetrakis (2-mercaptophenyl) porphyrin, 5,10,15,20-tetrakis ( 3-mercaptophenyl) porphyrin, 5,10,15,20-tetrakis (4 Mercaptophenyl) porphyrin, 5,10,15,20-tetrakis (2-aminophenyl) porphyrin, 5,10,15,20-tetrakis (3-aminophenyl) porphyrin, 5,10,15,20-tetrakis (4 -Aminophenyl) porphyrin, 5,10,15,20-tetrakis (2-hydroxyphenyl) porphyrin, 5,10,15,20-tetrakis (3-hydroxyphenyl) porphyrin, 5,10,15,20-tetrakis ( 4-hydroxyphenyl) porphyrin, [5,10,15-tris (2-thiofuryl) -20-mono (phenyl)] porphyrin, [5,10,15-tris (3-thiofuryl) -20-mono (phenyl) ] Porphyrin, [5,10-bis (2-thiofuryl) -15,20 Di (phenyl)] porphyrin, [5,10-bis (3-thiofuryl) -15,20-di (phenyl)] porphyrin, [5,15-bis (2-thiofuryl) -15,20-di (phenyl) ] Porphyrin, [5,15-bis (3-thiofuryl) -15,20-di (phenyl)] porphyrin, [5-mono (2-thiofuryl) -10,15,20-tri (phenyl)] porphyrin, [ A preferred example is 5-mono (3-thiofuryl) -10,15,20-tri (phenyl)] porphyrin.

  The ligand represented by the compound L represented by the chemical formula (II) can be appropriately selected and used. For example, imidazole derivatives, pyridine derivatives, aniline derivatives, histidine derivatives, trimethylamine derivatives, thiophenol derivatives. Examples include cysteine derivatives, methionine derivatives, benzoic acid derivatives, acetic acid derivatives, phenol derivatives, and aliphatic alcohol derivatives.

  The imidazole derivative is not particularly limited and can be appropriately selected and used. Examples thereof include methylimidazole, ethylimidazole, propioimidazole, dimethylimidazole, and benzimidazole.

  The pyridine derivative is not particularly limited and can be appropriately selected and used. Examples thereof include methylpyridine, methylpyridine acetate, nicotinamide, pyridazine, pyrimidine, pyrazine, and triazine.

  The aniline derivative is not particularly limited and can be appropriately selected and used. Examples thereof include aminophenol and diaminobenzene.

  The histidine derivative is not particularly limited and can be appropriately selected and used. Examples thereof include histidine methyl ester, histamine, hipryl-histidine-leucine and the like.

  The trimethylamine derivative is not particularly limited and can be appropriately selected and used. Examples thereof include triethylamine and tripropylamine.

  The thiophenol derivative is not particularly limited and can be appropriately selected and used. Examples thereof include thiocresol, mercaptobenzoic acid, aminothiophenol, benzenedithiol, and methylbenzenedithiol.

  The cysteine derivative is not particularly limited and can be appropriately selected and used. Examples thereof include cysteine methyl ester and cysteine ethyl ester.

  The methionine derivative is not particularly limited and can be appropriately selected and used. Examples thereof include methionine methyl ester and methionine ethyl ester.

  The benzoic acid derivative is not particularly limited and can be appropriately selected and used. Examples thereof include salicylic acid, phthalic acid, isophthalic acid, terephthalic acid and the like.

  The acetic acid derivative is not particularly limited and can be appropriately selected and used. Examples thereof include trifluoroacetic acid, mercaptoacetic acid, propionic acid, and tangled acid.

  The phenol derivative is not particularly limited and can be appropriately selected and used. Examples thereof include cresol and dihydroxybenzene.

  The aliphatic alcohol derivative is not particularly limited and can be appropriately selected and used. Examples thereof include ethyl alcohol and propyl alcohol.

  The method for adding the combustible liquid containing the metalloporphyrin complex can be appropriately selected and applied. For example, the metal porphyrin complex alone or the metal porphyrin complex dissolved in a solvent can be added as a flammable liquid. Alternatively, a method of confining the metal porphyrin complex in the capsule can also be employed.

  It is sufficient if the combustible liquid contains a metalloporphyrin complex, and it is preferable that the amount is as large as the main component.

  Although it may be used for combustion in which combustible liquids such as waste oil that are no longer needed are incinerated, it can also be applied to other combustion reactions. It is added at the time of combustion for the purpose of warming heating equipment such as fireplaces and stoves, and heat energy is converted into other energy (for example, thermal power generation that obtains electric energy from heat energy or an engine such as an automobile that converts heat energy into kinetic energy) It may be added at the time of combustion caused by the mechanism). The combustible liquid can be appropriately selected and used without particular limitation as long as it combusts. By including metal porphyrin in the flammable liquid, it is possible to reduce the amount of carbon dioxide emitted in the use of the flammable liquid. Therefore, it can greatly contribute to the reduction of the amount of carbon dioxide required by the above-mentioned Kyoto Protocol. If the amount of carbon dioxide emission is suppressed, it can greatly contribute to the reduction of carbon dioxide.

  In the present embodiment, it is preferable that a capsule composed of a nuclear material and an outer shell material including the core material is used, and the metal porphyrin is contained in the nuclear material. By doing in this way, the said granular material is disperse | distributed uniformly in a combustible liquid. Here, in order to disperse more suitably, the outer shell material has an affinity with the combustible liquid having affinity with the combustible liquid than the nuclear material and with the nuclear material with respect to the combustible liquid. An affinity substance containing a nuclear substance affinity substance is preferable because it contributes to uniform dispersion.

  When uniform dispersibility is improved, the amount of metal porphyrin used to obtain the same effect can be reduced. Therefore, a significant cost reduction can be realized by a significant decrease in the amount of metal porphyrin used, and a great economic contribution effect can be obtained. Further, when it is desired to refrain from using the metal porphyrin as much as possible, for example, when the metal porphyrin has some influence on the environment, it greatly contributes to the reduction of the amount of use, and as a result, it can make a great contribution to solving the global environmental problems.

  Examples of the outer shell material include surfactants and amphiphilic lipids. The amphiphilic lipid is selected from the group consisting of neutralized anionic lipids, amphoteric lipids and alkylsulfonic acid derivatives, and examples thereof include phospholipids and glycolipids described later.

  Neutralized anionic lipids are, for example, alkali metal salts of dicetyl phosphate, in particular sodium and potassium salts; alkali metal salts of dimyristyl phosphate, in particular sodium and potassium salts; alkali metal salts of cholesterol sulfonate, in particular Sodium salt; alkali metal salt of cholesterol phosphate, especially sodium salt; monosodium salt or disodium salt of acylglutamic acid, especially monosodium salt or disodium salt of N-stearoylglutamic acid; and sodium phosphatidic acid Things.

  When the functional material described above is a capsule containing a metal porphyrin as a core substance, the functional material is uniformly dispersed by the capsule, so the amount of the functional material used to obtain the same function is reduced. It can provide a great economic contribution and a great contribution to solving global environmental problems.

  The surfactant can be appropriately selected and used, but those suitable for emulsification are preferable, for example, phosphoric acid monoester, phosphoric diester, polyoxyethylene sorbitan monooleate, polyoxyethylene lauryl Examples include ether, polyethylene glycol monolaurate, and quaternary ammonium salts. Polylactic acid, rice wax, soybean lecithin, and phospholipid are preferred.

  For example, oleic acid, fatty acid polyhydric alcohol ester type nonionic surfactant such as sorbitan monolaurate, monooleate, monostearate or monopalmitate, sorbitan tristearate or trioleate, polyoxy of fatty acid polyhydric alcohol ester Ethylene adducts, polyacrylic acid, polymethacrylic acid, copolymers of polyacrylic acid and polymethacrylic acid, water-soluble polymers containing sulfonic acid groups such as sulfoethyl acrylate, sulfoethyl methacrylate or sulfopropyl methacrylate. And polymers of N- (sulfoethyl) -maleimide, 2-acrylamido-2-alkylsulfonic acid, styrene sulfonic acid and vinyl sulfonic acid, polyoxyethylene sorbitan Nolaurate, monooleate, monostearate, monopalmitate, tristearate or trioleate, polyethylene glycol fatty acid esters such as polyoxyethyl stearate, polyethylene glycol 400 stearate, polyethylene glycol 2000 stearate, D-α-tocopherol, DL- α-tocopherol, D-α-tocopherol acetate, DL-α-tocopherol acetate, ascorbyl palmitate, glycerides of vitamin F; vitamin Ds, especially vitamin D2 and vitamin D3; retinol, retinol esters (palmitate retinol ester and Retinol propionate), β-carotene, D-panthenol, farnesol, farnesyl acetate; rich in essential fatty acids Oil, in particular jojoba oil and black currant oil; 5-n-octanoylsalicylic acid, salicylic acid; α-hydroxy acids such as alkyl esters of citric acid, lactic acid and glycolic acid; asiatic acid, madagascar acid , Asiaticoside, total extract of Centella asiatica, β-glycyrrhetinic acid, α-bisabolol; ceramides, especially 2-oleoylamino-1,3-octadecane; phytantriol, sphingomyelin from milk Phospholipids derived from marine products rich in polyunsaturated essential fatty acids, ethoxyquin, mannen wax extract, perfume oil extract, quercetin, etc., short chain (C1-C6) alcohols such as ethanol; polyols such as glycols, In particular, 1,3-butylene glycol, propylene glycol, dipropylene glycol, isoprene glycol or hexylene glycol, glycerin, polyglycerin, and sorbitol can be exemplified.

  Examples of lipophilic surfactants include sucrose distearate, diglyceryl distearate, tetraglyceryl tristearate, decaglyceryl destearate, diglyceryl monostearate, hexaglyceryl tristearate, decaglycerin pentastearate, Sorbitan monostearate, sorbitan tristearate, diethylene glycol monostearate, esters of glycerin, palmitic acid and stearic acid, polyoxyethylene 2EO monostearate (ie containing two ethylene oxide units), mono- and dibehenic acid Glycerin and pentaerythritol tetrastearate.

  Examples of hydrophilic surfactants include the following compounds: polyoxyethylene sorbitan monostearate 4EO, polyoxyethylene sorbitan tristearate 20EO, polyoxyethylene 8EO monostearate, hexaglyceryl monostearate, monostearic acid Mention may be made of polyoxyethylene 10EO, polyoxyethylene 12EO distearate and polyoxyethylene methylglucose 20EO distearate.

  Nonionic, anionic, cationic and amphoteric surfactants can be mentioned.

  Nonionic surfactants include, for example, EO addition type nonionic surfactants [for example, higher alcohols (C8-18, the same shall apply hereinafter), higher fatty acids (C8-24, the same shall apply hereinafter) or higher alkylamines (C8-24). ) EO adduct (molecular weight 158 to Mn 200,000); higher fatty acid ester of polyalkylene glycol (molecular weight 150 to Mn 6,000) which is an EO adduct of glycol; polyhydric alcohol (C2-18 divalent to octavalent) Or higher, eg, ethylene glycol, propylene glycol, glycerin, pentaerythritol and sorbitan) EO adducts of higher fatty acid esters (molecular weight 250-Mn 30,000); EO adducts of higher fatty acid amides (molecular weight 200-Mn 30,000); And polyhydric alcohols (as above) alkyl EO adduct of C3-60) ether (molecular weight 120-Mn30,000)], and polyhydric alcohol (C3-60) type nonionic surfactant [for example, fatty acid (C3-60) ester of polyhydric alcohol , Alkyl (C3-60) ethers and fatty acids (C3-60) alkanolamides of polyhydric alcohols].

  The surfactant may be anionic, cationic or amphoteric.

  Examples of the anionic surfactant include compounds other than the above (C1), such as carboxylic acids (for example, C8-22 saturated or unsaturated fatty acids and ether carboxylic acids) or salts thereof; sulfate salts [for example, higher alcohol sulfate salts ( For example, sulfate esters of C8-18 aliphatic alcohols) and higher alkyl ether sulfate esters [eg sulfate esters of EO (1-10 mol) adducts of C8-18 aliphatic alcohols]]; sulfonates [ C10-20, such as alkyl benzene sulfonates (eg sodium dodecylbenzene sulfonate), alkyl sulfonates, alkyl naphthalene sulfonates, dialkyl ester sulfosuccinates, hydrocarbon (eg alkane, α-olefin) sulfonates and Igepon T type] And phosphoric acid ester salts [e.g. higher alcohol (C8~60) EO adduct phosphoric acid ester salts and alkyl (C4~60) phenol EO adduct phosphoric acid ester salts], and. Examples of the salts include alkali metal salts, alkaline earth metal salts, ammonium salts, alkylamine (C1-20) salts and alkanolamine (C2-12, such as mono-, di- and triethanolamine) salts. It is done.

  Cationic surfactants include quaternary ammonium salt types [eg, tetraalkyl (C4-100) ammonium salts (eg, lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide and stearyltrimethylammonium bromide), Alkyl (C3-80) benzylammonium salts (eg lauryldimethylbenzylammonium chloride (benzalkonium chloride), alkyl (C2-60) pyridinium salts (eg cetylpyridinium chloride), polyoxyalkylene (C2-4) trialkylammonium salts (Eg, polyoxyethylenetrimethylammonium chloride) and sapamine type quaternary ammonium salts (eg, stearamide ester) Rudiethylmethyl ammonium methosulfate)]; and amine salt forms [eg higher aliphatic amines (C12-60, eg laurylamine, stearylamine, cetylamine, hardened tallow amine and rosinamine) inorganic acids (eg hydrochloric acid, sulfuric acid, nitric acid and Phosphoric acid) salts or organic acids (C2-22, eg acetic acid, propionic acid, lauric acid, oleic acid, benzoic acid, succinic acid, adipic acid and azelaic acid) salts, EO adducts of aliphatic amines (C1-30) Inorganic acids (above) or organic acids (above) and tertiary amines (C3-30, eg triethanolamine monostearate and stearamide ethyl diethyl methylethanolamine) Or salt of organic acid (above)].

  Examples of amphoteric surfactants include amino acid type amphoteric surfactants [for example, higher alkylamine (C8-24) sodium propionate], betaine type amphoteric surfactants [for example, alkyl (C12-18) dimethylbetaine], sulfate ester salts Type amphoteric surfactants [e.g. sulfate sodium salt of higher alkylamine (C8-24) and hydroxyethyl imidazoline sulfate sodium salt], sulfonate type amphoteric surfactants (e.g. pentadecyl sulfotaurine and imidazoline sulfonic acid) and Phosphate ester type amphoteric surfactants [for example, phosphate ester amine salts of glycerin higher fatty acid (C8-24) esterified products].

  The molecular weight regulator or the polymer chain transfer agent can be appropriately selected and used. For example, mercaptan, mercaptoethanol, mercaptopropanol, mercaptobutanol, n-dodecyl mercaptan, mercaptosuccinic acid, mercaptopropionic acid, mercaptoglycerin, Mercaptoacetic acid, thioglycolic acid ester such as hexyl thioglycolate, mercaptoglycol silane such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyl-methyldimethoxysilane, ether, dioxane, tetrahydrofuran, tetrahydrofurfuryl alcohol, tetrahydrofuracetic acid Furyl esters, alcohols such as isopropanol, n-butanol and n-decanol and aromatic hydrocarbons such as iso It can be cited as an example Ropirubenzoru.

  The radical-forming polymerization initiator can be appropriately selected and used. For example, t-butylperoxyneodecanoate, t-amylperoxypivalate, dilauroyl peroxide, t-amylperoxy-2-ethylhexanoate 2,2'-azobis- (2,4-dimethyl) valeronitrile, 2,2'-azobis- (2-methoxybutyronitrile), dibenzoyl peroxide, t-butylper-2-ethylhexanoate, di T-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and cumol hydroperoxide. The radical initiators used with preference are di (3,5,5-trimethylhexanoyl) -peroxide, 4,4′-azobisisobutyronitrile, t-butylperpivalate and dimethyl-2,2 ′. An example is azobisisobutyrate.

  In addition, if it is a combustible liquid in which capsules containing a metal porphyrin complex and a redox polymer as a functional material and containing these as core materials are dispersed, carbon dioxide generated when this combustible liquid is burned However, a smaller amount of metal porphyrin complex and redox polymer may be used than when no encapsulation is used. These functional materials are usually expensive, and the most important proposition is to reduce the amount used and to reduce the price. Since the amount used can be reduced and the price can be reduced in this way, the capsule-dispersed combustible liquid can be provided at a low price. As a result, the combustible liquid on the market is replaced with the combustible liquid, which greatly contributes to the reduction effect of carbon dioxide, and the environmental and economic effects due to the reduction of carbon dioxide are remarkable.

  Such capsules are preferably liposomes. Liposomes can further contribute to uniform dispersion and the like, and can further enhance environmental, economic, and physical effects. By securing the dispersibility with such liposomes, the amount of metal porphyrin used can be further reduced and the price can be reduced, so that the combustible liquid in which the liposomes are dispersed can be provided at a low price. As a result, the combustible liquid in the market is further replaced with the combustible liquid, which greatly contributes to the reduction effect of carbon dioxide, and the environmental and economic benefits due to the reduction of carbon dioxide are further remarkable. Liposomes are used as cosmetics and foods, and can provide flammable liquids that can contribute to the next generation of environmental society with little impact on health and the environment.

  In this embodiment, the combustible liquid serving as a dispersion medium is, for example, fuel oil, crude oil, petroleum products (volatile oil, kerosene, naphtha, light oil, heavy oil, etc.), petrochemical raw materials, liquefied natural gas, gasoline, kerosene, animals and plants Oils, oil products, machine oils, flammable organic solvents, solvents, tar pitches, mineral oils, flammable liquids of Class 4 of the Fire Service Act (including liquids mixed with non-flammable liquids) These waste oils can be exemplified.

  Examples of the flammable liquid include a liquid having an ignition point of 100 ° C. or lower or a flash point of −20 ° C. or lower and a boiling point of 40 ° C. or lower, ether, carbon disulfide, collodion, acetaldehyde, propylene oxide, pentane, acetone, etc. , Gasoline, petroleum benzine, ligroin, dioxane, benzene, toluene, petroleum ether, hexane, tetrahydrofuran, isopropyl ether, acrylonitrile, ethylamine, ethyl acetate, methyl ethyl ketone and other primary petroleum, methyl alcohol, ether alcohol, isopropyl alcohol and other alcohols , Kerosene, light oil, chlorobenzene, ethylbenzene, styrene, xylene, ethyl cellosolve, formic acid, acetic acid, turpentine oil, camphor oil, and other second petroleum oils, heavy oil, creosote oil, glycerin, aniline, ni 3rd petroleum such as lobenzene, ethanolamine, ethylene glycol, cresol, 4th petroleum such as gear oil, cylinder oil, lubricating oil, turbine oil, machine oil, motor oil, coconut oil, olive oil, castor oil, peanut oil And vegetable oils such as rapeseed oil, sesame oil, and cottonseed oil, and mixtures thereof.

  The oil product is not particularly limited, and examples thereof include lubricating oils such as engine oil and gear oil, cutting oils, a mixture of a plurality of base oils, and those obtained by adding an additive thereto. Examples of the base oil include chemical synthetic oil, partially synthetic oil, high viscosity index oil, mineral oil, and high VI mineral oil.

  The waste oil is not particularly limited. For example, lubricating oil, insulating oil, cleaning oil and cutting oil, waste flammable liquid, waste solvents, tar pitches, mineral oil, animal and vegetable oils and fats, and the above examples The oil related to the oil that has become waste. Note that “waste” means a product that has been used for a time, quality, and other reasons.

"Production method of flammable liquid"
The combustible liquid may be produced by dissolving metal porphyrin with the combustible liquid, or may be produced by dispersing in a combustible liquid. If the metal porphyrin is produced by dissolving it with a flammable liquid, it is often preferable in terms of cost because only the dissolving step is required.

  Next, an embodiment as an example of manufacturing by dispersing in a flammable liquid will be described. A method for producing a flammable liquid will be described by exemplifying a method in which a liposome having a particle size of 50 to 800 nm having a metalloporphyrin complex as a core substance is dispersed in a resin. That is, since it is suitable in this embodiment, the following supercritical carbon dioxide method is used to disperse this in a flammable liquid using a metalloporphyrin complex as an encapsulating substance as a core substance and a liposome as a capsule made of lipid as an outer shell substance. I am letting.

(Preparation of liposome)
First, a liposome having a particle size of 50 to 800 nm dispersed in an aqueous phase as an aqueous solution is prepared. The outer shell material of the liposome is a lipid or a fat, which can be appropriately selected from these, and is preferably a phospholipid or a glycolipid. More preferably, the phospholipid or glycolipid is a compound capable of forming a lipid bilayer. The lipid is an affinity substance containing a combustible liquid affinity substance having an affinity for the combustible liquid rather than a nuclear substance and a nuclear substance affinity substance having an affinity for the nuclear substance than the combustible liquid. Representative examples of the affinity substance include the above-mentioned surfactants and surfactants such as emulsifiers.

  Phospholipids are also referred to as phosphatides, and it is considered as a general definition of a group of substances having a phosphate ester and a CP bond among complex lipids. Examples of phospholipids include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, egg yolk lecithin, hydrogenated egg yolk lecithin, glycerophospholipid such as soybean lecithin, hydrogenated soybean lecithin, sphingomyelin And sphingophospholipids such as ceramide phosphorylethanolamine and ceramide phosphorylglycerol.

  Examples of glycolipids include, for example, glycerolipids such as digalactosyl diglyceride and galactosyl diglyceride sulfate, galactosylceramide, galactosylceramide sulfate, lactosylceramide, ganglioside G7, ganglioside G6, ganglioside G4 and other sphingoglycolipids. Can do.

  The state of the metal porphyrin complex which is the encapsulating substance which is the core substance of the liposome may be any of gas, liquid and solid.

The method for producing the liposome can be selected as appropriate, but for example, the following method can be employed as an example.
(1) An ultrasonic treatment method in which a lipid suspension is treated with ultrasonic waves.
(2) A surfactant removal method in which a mixed micelle of lipid and surfactant is formed to remove the surfactant.
(3) An organic solvent injection method in which lipids dissolved in an organic solvent are injected into a water tank to form liposomes at the interface between water and the organic solvent.
(4) A freeze-thaw method in which an aqueous solution in which lipids are suspended is frozen and then melted to form a lipid bilayer membrane, which is further freeze-thawed to form liposomes.
(5) A reverse phase evaporation method in which a small amount of an aqueous solvent is added to an organic solvent that does not dissolve in water, ultrasonic waves are applied to form a W / O emulsion (reverse micelle), and the organic solvent is removed under reduced pressure.
(6) A method using a supercritical fluid. The supercritical fluid is not particularly limited, and examples thereof include carbon dioxide, water, ethane, ethylene, propane, and nitrous oxide. A supercritical carbon dioxide method in which lipid is dissolved in a mixed fluid of carbon dioxide and ethanol, and an aqueous solution to be retained is stirred and injected in a decompression process is suitable.

  The supercritical carbon dioxide method can take various forms, but one example of this method will be described. Supercritical carbon dioxide and a co-solvent, if necessary, are pumped and passed through a column filled with phospholipids. . The phospholipid is transported to the pressure reducing valve in a state of being dissolved in a mixed fluid of carbon dioxide and a cosolvent, and is depressurized. Phospholipids are precipitated during the decompression process. At this time, an aqueous phase containing a water-soluble substance to be retained (in this embodiment, a metal porphyrin complex) is introduced through a pump and stirred by a mixer, whereby the liposomes are mixed. And a method of forming the film inside.

  In addition, an aqueous phase containing an encapsulating substance (in this embodiment, a metalloporphyrin complex) is added to a homogeneous mixed fluid of carbon dioxide and phospholipid or glycolipid under supercritical state or temperature or pressure conditions above the critical point. It is preferable that the liposome is produced by a supercritical carbon dioxide method enclosing a characteristic encapsulated substance. In this method, an aqueous phase containing a water-soluble or hydrophilic encapsulating substance is added to a mixture in which phospholipid is uniformly dissolved in carbon dioxide in a supercritical state or a temperature or pressure condition above the critical point, The object is to produce liposomes that encapsulate the encapsulated substance in one stage. Since the liposome produced by this method has high retention efficiency, it can encapsulate a larger amount of encapsulated substance than conventional liposomes. The carbon dioxide in the supercritical state means carbon dioxide in a supercritical state at a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa), Carbon dioxide under pressure means carbon dioxide under a condition where only the critical temperature or only the critical pressure exceeds the critical condition (however, the other does not exceed the critical condition). Hereinafter, it is considered as a definition that carbon dioxide under supercritical conditions or temperature or pressure conditions above the critical point is collectively referred to as “supercritical carbon dioxide”.

  The homogeneously mixed fluid that was initially transparent gradually becomes cloudy with the introduction of the aqueous phase (it is considered that reverse micelles are formed), and when the aqueous phase is further introduced, the water into the supercritical carbon dioxide (and reverse micelles) When the solubility limit is exceeded, a cloudy aqueous phase is formed at the bottom of the reaction vessel. After injecting the predetermined aqueous phase, a uniform liposome can be obtained by reducing the pressure.

  In preparing a homogeneous mixture of phospholipid and supercritical carbon dioxide, it is preferable to use a co-solvent. By adding a cosolvent to the system, it is possible to increase the solubility of the poorly soluble encapsulated material in supercritical carbon dioxide. Examples of the co-solvent include ethyl alcohol, polar solvent, dichloroethane, dichloromethane, and the like. In particular, when dichloroethane, dichloromethane, or the like is used, it is often preferable for solubility when a metal porphyrin is used as an encapsulating substance.

  The addition amount of the aqueous phase may be appropriately selected within a range where water can flow in with fluidity and a range in which the formation of liposomes is not inhibited.

  As a medium constituting the aqueous phase containing the encapsulated substance (in this embodiment, a metal porphyrin complex), water, tap water, distilled water, pure water, deep ocean water, ultrafiltered water, filtered water, groundwater, underground water , Desalted water, purified water (RO water, membrane treated water), rain water, well water, neutralized water, electrolyzed water, aqueous solution, and the like.

  The prepared liposomes may be dried and dispersed in a flammable liquid as solid liposome capsules.

  The method of drying into solid capsules can be selected and used as appropriate. For example, interfacial deposition method, interfacial reaction method, phase separation method, submerged drying method, melt dispersion cooling method, spray drying method, panning method Examples thereof include a coating method, a freeze-drying method, an air suspension coating method, a powder bed method, an interfacial polymerization method, an in-situ polymerization method, a liquid curing coating method, an orifice method, and an interfacial reaction method.

  The flammable liquid to which the metal porphyrin is added, including dissolution and dispersion in the form of granules such as liposomes according to the present embodiment, can be used according to its application, and carbon dioxide emissions can be reduced in the combustion and the like. .

  Examples will be described in detail below.

"Example 1"
A metal porphyrin complex was added to the flammable liquid exemplified in the above embodiment, and a combustion gas analysis test was performed (combustion gas generation method defined in JIS K 7217, carbon dioxide by gas chromatography (GC-TCD)) Quantity analysis method).

  As a result, when the metal porphyrin complex was added and incinerated, the amount of carbon dioxide could be reduced with respect to the same type of combustible liquid incinerated without adding the metal porphyrin complex.

"Example 2"
The same combustion gas analysis test as in Example 1 was performed on the combustible liquid exemplified in the above embodiment.

  As a result, when the metal porphyrin complex was added and incinerated, the amount of carbon dioxide could be reduced with respect to the same type of combustible liquid incinerated without adding the metal porphyrin complex.

"Example 3"
In Example 2, a capsule composed of a metal porphyrin as a dispersed phase as a core material and an outer shell material containing the core material was used.

  As a result, even when compared with Example 2, the amount of carbon dioxide could be further reduced by comparison with the same type of combustible liquid.

Example 4
In Example 3, the outer shell material has a flammable liquid affinity material having an affinity with the flammable liquid than the nuclear material, and a nuclear material affinity with an affinity for the nuclear material than the flammable liquid. It was set as the affinity substance containing a substance. A surfactant was used as the affinity substance.

  As a result, it was possible to further reduce the amount of carbon dioxide even when compared with Example 3 in comparison with the case where the same kind of combustible liquid was used.

"Example 5"
In Example 4, the system in which the metal porphyrin complex was included in the liposome was burned by the method defined in JIS K 7217, and measured by gas chromatography (GC-TCD).

  As a result, a carbon dioxide reduction effect was further obtained even when compared with Example 4 in the case of using the same kind of flammable liquid.

"Example 6"
About Examples 1-5, it burned by the method prescribed | regulated by JISK7217 about the system which used gasoline as a combustible liquid, and measured by the gas chromatograph method (GC-TCD).

  As a result, the carbon dioxide reduction effect was obtained in comparison with the case of using the same kind of gasoline.

"Example 7"
About Examples 1-5, it burned by the method prescribed | regulated by JISK7217 about the system using an oil product as a combustible liquid, and measured by the gas chromatograph method (GC-TCD).

  As a result, the carbon dioxide reduction effect was obtained in comparison with the case of using the same kind of oil product.

"Example 8"
About Examples 1-5, it burned by the method prescribed | regulated by JISK7217 about the system which used the flammable liquid as a combustible liquid, and measured by the gas chromatograph method (GC-TCD).

  As a result, a carbon dioxide reduction effect was obtained in comparison with the case of using the same kind of flammable liquid.

"Example 9"
In Examples 1 to 5, a system using waste oil as a flammable liquid was combusted by a method defined in JIS K 7217 and measured by a gas chromatographic method (GC-TCD).

  As a result, the carbon dioxide reduction effect was obtained in comparison with the case of using the same kind of waste oil.

Claims (5)

  A flammable liquid containing at least a metalloporphyrin complex. A flammable liquid according to claim 1,
The metal porphyrin complex is a combustible liquid contained in a granular material having a particle size of 50 to 800 nm. A flammable liquid according to claim 1 or 2,
The combustible liquid is a capsule composed of a core material and an outer shell material containing the core material,
The metal porphyrin complex is a flammable liquid that is contained in the nuclear material. A flammable liquid according to claim 3,
The outer shell material is
Combustibility which is an affinity substance including a combustible liquid affinity substance having an affinity with the combustible liquid rather than the nuclear substance and a nuclear substance affinity substance having an affinity with the nuclear substance than the combustible liquid. liquid. A flammable liquid according to any one of claims 1 to 4,
A flammable liquid in which the metalloporphyrin contained in a liposome is dispersed.