WO2010004872A1

WO2010004872A1 - Cold flow improver for biodiesel fuel

Info

Publication number: WO2010004872A1
Application number: PCT/JP2009/061488
Authority: WO
Inventors: 由紀杉浦; 幸也森泉; 佳秀齋尾; 真史飯野
Original assignee: 株式会社Adeka
Priority date: 2008-07-10
Filing date: 2009-06-24
Publication date: 2010-01-14
Also published as: CN101910379B; JPWO2010004872A1; CN101910379A; JP5450411B2

Abstract

Disclosed is a cold flow improver which can improve the low-temperature flow properties of a biodiesel fuel efficiently. The cold flow improver is characterized by comprising a polymer containing 50 mass% or more of a polyester in the molecule, wherein the polyester is a product of the reaction between a compound represented by general formula (1)[wherein AH₂ represents a hydrocarbon group having 2 to 300 carbon atoms; and g represents an average polymerization degree and is a number of 1 to 1000] and/or general formula (2) [wherein AH₂ represents a hydrocarbon group having 2 to 300 carbon atoms; and h represents an average polymerization degree and is a number of 1 to 1000] with at least one polyhydric alcohol (Y) represented by general formula (3) (Y) R－(OH) _n (3) [wherein R represents an oxygen atom, or a hydrocarbon group having 2 to 500 carbon atoms which may contain a nitrogen atom; and n represents a number of 2 or greater].

Description

Low temperature fluidity improver for biodiesel fuel

The present invention relates to a low-temperature fluidity improver for biodiesel fuel containing a fatty acid methyl ester.

Fossil fuels such as gasoline, light oil, and oil are mainly used as fuel oil, but when these fuels are consumed, carbon dioxide is released into the atmosphere, which is a major cause of environmental problems such as global warming. It is thought that. For these reasons, various methods have been considered to reduce the release of carbon dioxide into the environment.
One method has been proposed to use biofuel. Biofuel is fuel oil obtained mainly from plants, and is used as fuel for automobiles or the like by mixing ethanol, methanol, fatty acid methyl ester, etc. with 100% or fossil fuel. Because biofuel is made from plants that consume carbon dioxide in the atmosphere, even if biofuel is released into the atmosphere as carbon dioxide by combustion, new plants that are the source of biofuel consume that carbon dioxide , Carbon dioxide in the atmosphere does not increase (carbon dioxide circulation). Such biofuels have been started in various forms as described above, but can be directly applied to existing engine systems and do not require engine improvements. The study of biodiesel fuel containing most biofuels is most advanced.

For example, Patent Document 1 discloses a biodiesel fuel composition in which an antioxidant is added to biodiesel fuel, and the biodiesel fuel contains 1% or more of oleic acid methyl ester and / or linoleic acid methyl ester, As a main component, it comprises one or more fatty acid methyl esters having C4 to C25 carbon atoms, and the antioxidant comprises a natural component and / or a synthetic component, and is based on the total weight of the fatty acid methyl ester. A biodiesel fuel composition characterized in that it is added in a proportion of 0.001% to 5%; a method of using said biodiesel fuel composition, wherein A method of using a biodiesel fuel composition characterized by mixing at a volume ratio of 1 to 100% is disclosed.

However, biodiesel fuel containing fatty acid methyl ester has a high pour point, and the fluidity of the fuel deteriorates when the fatty acid methyl ester is blended at a high concentration or when used in cold regions even at low concentrations. In order to spread the biodiesel fuel, it was necessary to improve the low temperature fluidity of the biodiesel fuel.

Under such circumstances, various low temperature fluidity improvers are known for existing diesel fuels. For example, Patent Document 2 discloses that compound A represented by the following general formula (A) and compound B represented by the following general formula (B) have a weight ratio (compound A) :( compound B) of 1:99. Or low-temperature fluidity improver for fuel oil to be contained so as to be 50:50:

(In the formula, n represents an integer of 2 or more, and X ¹ to X ⁸ each independently represent hydrogen, a straight-chain hydrocarbon or a branched hydrocarbon group, or a cyclohydrocarbon group having 3 or more carbon atoms.)

(In the formula, any one of X ⁹ and X ¹⁰ is a linear or branched hydrocarbon group having 8 to 24 carbon atoms, the other is hydrogen, and X ¹¹ is NR ¹ R ² or NHR ³ , X ¹² is H ⁺ , HN ⁺ HR ⁴ R ⁵ or HN ⁺ H ₂ R ⁶ , and R ¹ to R ⁶ each independently represents a hydrocarbon group having 8 to 24 carbon atoms)
Is disclosed.

Patent Document 3 discloses (A) a fatty acid selected from linear saturated fatty acids having 8 to 28 carbon atoms and linear unsaturated fatty acids having 8 to 28 carbon atoms, and (B) a pour point depressant and Oil improver for low sulfur gas oil containing at least one modifier selected from low temperature fluidity improver and having a sulfur content of 0.05% by weight or less; pour point depressant is chlorinated paraffin and naphthalene The oil improver for low sulfur gas oil, which is at least one selected from condensate, condensate of chlorinated paraffin and phenol, polyalkyl methacrylate, polybutene, polyalkyl styrene, polyvinyl acetate and polyalkyl acrylate; low temperature fluidity Before the improver is at least one selected from ethylene-vinyl acetate copolymer, ethylene-alkyl acrylate and alkenyl succinic acid amide Low sulfur diesel fuel for the oiliness improver is disclosed.

JP 2007-016089 A Japanese Patent Laid-Open No. 2005-187581 Japanese Patent Laid-Open No. 10-110175

However, low-temperature fluidity improvers such as those described in Patent Documents 2 and 3 described above are not very effective for biodiesel fuel, and low-temperature fluidity improvers for biodiesel fuel are desired.

Therefore, an object of the present invention is to provide a low temperature fluidity improver that can efficiently improve the low temperature fluidity of biodiesel fuel.

Thus, the present inventors have intensively studied, and found a low-temperature fluidity improver that can greatly improve the low-temperature fluidity of biodiesel fuel, resulting in the present invention.
That is, the present invention relates to a compound (X) represented by the following general formula (1) and / or general formula (2):

(In the formula, AH ₂ represents a hydrocarbon group having 2 to 300 carbon atoms, g represents an average degree of polymerization, and represents a number of 1 to 1000.)

(In the formula, AH ₂ represents a hydrocarbon group having 2 to 300 carbon atoms, h represents an average degree of polymerization, and represents a number of 1 to 1000.)
One or more polyhydric alcohols (Y) represented by the following general formula (3)
R- (OH) _n (3)
(In the formula, R represents a hydrocarbon group having 2 to 500 carbon atoms which may contain an oxygen atom or a nitrogen atom, and n represents a number of 2 or more.)
It is a low temperature fluidity improver for biodiesel fuel, which is a polymer containing 50% by mass or more of polyester, which is a reaction product thereof, in the molecule.

The effect of the present invention is to provide a low-temperature fluidity improver that can efficiently improve the low-temperature fluidity of biodiesel fuel.

Compound (X) that can be used in the present invention can be represented by the following general formula (1) or (2):

(In the formula, AH ₂ represents a hydrocarbon group having 2 to 300 carbon atoms, h represents an average degree of polymerization, and represents a number of 1 to 1000.)

Examples of the dicarboxylic acid represented by the general formula (1) include alkanedicarboxylic acids such as succinic acid, glutanic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid when the value of g is 1. Benzene dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; alkene dicarboxylic acids such as maleic acid; and compounds obtained by hydrolysis after addition reaction of olefin or polyolefin with maleic anhydride.
When the value of g is 2 or more, polyalkanedicarboxylic acid such as polysuccinic acid, polyglutanic acid, polyadipic acid, polypimelic acid, polysuberic acid, polyazelinic acid, polysebacic acid; polymerization reaction product of maleic anhydride and olefin or polyolefin And the like obtained by hydrolysis.

In addition, as the acid anhydride represented by the general formula (2), for example, when the value of h is 1, succinic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, suberic anhydride, azelaic anhydride , Sebacic anhydride, phthalic anhydride, maleic anhydride, olefins of maleic anhydride, polyolefin adducts, and the like.
When the value of h is 2 or more, polyalkanedicarboxylic acid such as polysuccinic anhydride, polyglutanic anhydride, polyadipic anhydride, polypimelic anhydride, polysuberic anhydride, polyazelaic anhydride, polysebacic anhydride, etc. And a polymerization reaction product of maleic anhydride and olefin or polyolefin.

Examples of the olefin to be reacted with an acid anhydride such as maleic anhydride include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-decene, Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, styrene, vinylcyclohexane, 1,3-butadiene, Examples include 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,7-octadiene, cyclohexadiene, and the like. Examples of the polyolefin include the above-mentioned olefins, preferably olefins having 2 to 16 carbon atoms. One or more of It is sufficient to react in a way.

As a method of adding an olefin or polyolefin to an acid anhydride, for example, maleic acid, a known method may be used. For example, 1 mol of olefin or polyolefin is added at 180 to 350 ° C. with respect to 1 mol of maleic anhydride. The alkenyl succinic anhydride [h value of the general formula (2) is 1] can be obtained by heating for 2 to 30 hours, and the obtained alkenyl succinic anhydride is hydrolyzed by a known method. Thus, alkenyl succinic acid [the value of g in the general formula (1) is 1] which is a dicarboxylic acid can be obtained. Since the following polymerization reaction may proceed during the heating reaction, a polymerization inhibitor such as hydroquinone or a phenolic compound may be added.

As a method for polymerization reaction of olefin or polyolefin with acid anhydride, for example maleic acid, a known method may be used. For example, 1 mol of olefin or polyolefin and a polymerization initiator are mixed with 1 mol of maleic anhydride. The polyalkenyl succinic anhydride can be obtained by heating reaction at 180 to 350 ° C. for 2 to 30 hours, and the resulting polyalkenyl succinic anhydride is hydrolyzed by a known method to obtain a polycarboxylic acid. A polyalkenyl succinic acid can be obtained. The degree of polymerization of these polymers is represented by g or h in the general formulas (1) and (2), and the values of g and h are 2 to 1000, but show good performance as a low temperature fluidity improver. Therefore, the values of g and h are preferably 2 to 500, more preferably 2 to 300, and still more preferably 2 to 100. Examples of the polymerization initiator include azobisisobutyronitrile and benzoyl peroxide.

In addition, when the performance as a low temperature fluidity improver of a compound having a g or h value of 1 (addition reaction product) and a compound having a g or h value of 2 or more (polymerization reaction product) is compared, The performance is generally better, but the mixture of the addition reaction product and the polymerization reaction product has better performance.

In the general formulas (1) and (2), AH ₂ is a hydrocarbon group having 2 to 300 carbon atoms. However, since the performance as a low-temperature fluidity improver is good, 2 to 100 carbon atoms are present. 2-50 are more preferable, and 2-20 are still more preferable. When the carbon number of A is less than 2 or more than 300, sufficient performance as a low temperature fluidity improver cannot be obtained. In addition, since it is easy to set A to the preferred number of carbon atoms, dicarboxylic acid is a compound obtained by subjecting maleic anhydride to addition reaction of olefin or polyolefin and then hydrolyzing, and maleic anhydride is polymerized with olefin or polyolefin. The compound obtained by hydrolysis after the reaction is preferred, and the anhydride is preferably an olefin of maleic anhydride or an adduct of polyolefin and a polymer of maleic anhydride and olefin or polyolefin.

The polyhydric alcohol (Y) that can be used in the present invention can be represented by the following general formula (3):
R- (OH) _n (3)
(In the formula, R represents a hydrocarbon group having 2 to 500 carbon atoms which may contain an oxygen atom or a nitrogen atom, and n represents a number of 2 or more.)

The compound of the general formula (3) may be any compound as long as it has a hydrocarbon group having 2 to 500 carbon atoms and n is 2 or more, that is, contains 2 or more hydroxyl groups, such as ethylene glycol. , Diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, tri Butylene glycol, polybutylene glycol, 1,5-pentanediol, neopentyl glycol, isoprene glycol (3-methyl-1,3-butanediol), 1,2-hexanediol, 1,6-hexanediol, 3-methyl -1, -Pentanediol, 1,2-octanediol, octanediol (2-ethyl-1,3-hexanediol), 2-butyl-2-ethyl-1,3-propanediol, 2,5-dimethyl-2,5 -Hexanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-tetradecanediol, 1,2-hexadecanediol, 1,2-octadecanediol, 1,12-octadecanediol, 1,2- Cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, sorbide, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne -3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol Dihydric alcohols such as bis (hydroxymethyl) benzene, N-methyldiethanolamine, N-ethyldiethanolamine; glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 2-methyl-1,2, 3-propanetriol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 1,3,5-pentanetriol, 2,3,4-pentanetriol, 2-methyl-2,3,4 -Butanetriol, trimethylolethane, 2,3,4-hexanetriol, 2-ethyl-1,2,3-butanetriol, trimethylolpropane, 4-propyl-3,4,5-heptanetriol, pentamethylglycerin (2,4-dimethyl-2,3,4-pentanetriol), triethanolamine, tri Trihydric alcohols such as isopropanolamine; erythritol, pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1 , 3,4,5-hexanetetrol, diglycerin, ditrimethylolpropane, sorbitan, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxyethyl) tetrahydric alcohols such as ethylenediamine; pentahydric alcohols such as adonitol, arabitol, xylitol, triglycerin; hexavalent alcohols such as dipentaerythritol, sorbitol, mannitol, inditol, inositol, dulcitol, talose, allose, etc. Can be mentioned.

Also, a compound obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide or a cyclic ether such as polytetrahydrofuran to the polyhydric alcohol can be used.

The polyhydric alcohol has 2 to 500 carbon atoms, preferably 2 to 100, more preferably 2 to 50, and further preferably 2 to 20. When the carbon number exceeds 1 or 500, sufficient performance as a low temperature fluidity improver cannot be obtained. When n is 1, that is, the monovalent alcohol does not become a polyester even when reacted with the compound (X), and the resulting compound does not have performance as a low-temperature fluidity improver.

In the present invention, the polyhydric alcohol (Y) to be reacted with the compound (X) is a dihydric or higher alcohol, and when the valence of the alcohol is increased, the viscosity of the resulting polyester is increased and handling becomes difficult. Since solubility in biodiesel fuel may decrease, divalent to tetravalent alcohols (n = 2 to 4) are preferable, and divalent (n = 2) or trivalent (n = 3) alcohols are more preferable. Divalent alcohols are preferred and most preferred.

The reaction ratio of compound (X) to polyhydric alcohol (Y) is not particularly limited, but the hydroxyl group of polyhydric alcohol (Y) is 0.1 to 1.5 with respect to 1 mol of acyl group of compound (X). It is preferable to mix and react so as to have a molar ratio, more preferable to mix and react so as to be 0.2 to 1.0 mol, It is more preferable to react. When the ratio of the hydroxyl group is too high or the ratio of the acyl group is too high, sufficient performance as a low temperature fluidity improver may not be obtained.

When the compound (X) and the polyhydric alcohol (Y) are reacted, a polyester bonded by an ester bond is formed. Any known method can be used to obtain this polyester. For example, a strong acid such as sulfuric acid or toluenesulfonic acid; titanium tetrachloride, hafnium chloride, zirconium chloride, aluminum chloride, gallium chloride, chloride Metal halides such as indium, iron chloride, tin chloride and boron fluoride; hydroxides and alcoholates of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, sodium methylate and sodium carbonate, Carbonates; metal oxides such as aluminum oxide, calcium oxide, barium oxide, sodium oxide; organometallic compounds such as tetraisopropyl titanate, dibutyltin dichloride, dibutyltin oxide and the like, and 2-30 at a reaction temperature of 120-300 ° C. You can dehydrate for a long time, if necessary It may be 圧脱 water.

In the above reaction, when the number of moles of the acyl group of the compound (X) and the hydroxyl group of the polyhydric alcohol (Y) is the same, when the dicarboxylic acid of the general formula (1) is used, 2 moles of water per mole of the dicarboxylic acid As a by-product, when the acid anhydride of the general formula (2) is used, 1 mol of water is by-produced with respect to 1 mol of the acid anhydride. Therefore, it is preferable to use an acid anhydride for the compound (X) from the viewpoint of production efficiency such as a dehydration step. The catalyst may or may not be used, but it is preferable not to use a catalyst because the step of removing the catalyst can be omitted.

The polyester obtained by the above reaction is a linear polyester if the polyhydric alcohol (Y) is divalent when the g value in the general formula (1) and the h value in the general formula (2) are 1. If the polyhydric alcohol (Y) is trivalent or more, a network-like polyester is mainly formed (both may produce a cyclic polyester). The polyester when the divalent polyhydric alcohol (Y) is used preferably has a polyester unit represented by the following general formula (4):

(In the formula, A represents a hydrocarbon group having 2 to 300 carbon atoms, and R ′ represents a hydrocarbon group having 2 to 500 carbon atoms which may contain an oxygen atom or a nitrogen atom.)

On the other hand, when the value of g or h is 2 or more, a reticulated polyester is formed regardless of the valence of the polyhydric alcohol (Y), but as the valence of (Y) increases, the polyester form Is complicated.
If the form of the polyester is complicated, the viscosity may increase and handling may be difficult, or the solubility in biodiesel fuel may decrease, so the polyhydric alcohol (Y) is preferably divalent. The polyester when the divalent polyhydric alcohol (Y) is used preferably has a polyester unit represented by the following general formula (5):

The weight average molecular weight of the polyester varies depending on the amount and type of the catalyst, the reaction temperature, the reaction time, etc., but the value of g in the general formula (1) or the value of h in the general formula (2) is 1, and the polyhydric alcohol ( When Y) is divalent, it is generally 300 to 50,000, and when polyhydric alcohol (Y) is trivalent or more, it is generally 500 to 500,000.

When the value of g in the general formula (1) or the value of h in the general formula (2) is 2 to 1000 and the polyhydric alcohol (Y) is divalent, the polyhydric alcohol (Y ) Is trivalent or more, it is generally 3000 to 1000000.

The molecular weight is not limited, but if the molecular weight is too small, the effect as a low-temperature fluidity improver will be low, and if the molecular weight is too high, handling may be difficult or it may not dissolve in biodiesel fuel. When the value of g in (1) or the value of h in general formula (2) is 1, the weight average molecular weight is preferably 300 to 100,000, more preferably 500 to 50,000, and still more preferably 1,000 to 30,000. What is necessary is just to superpose | polymerize.

When the value of g in the general formula (1) or the value of h in the general formula (2) is 2 to 1000, the weight average molecular weight is preferably 500 to 500,000, more preferably 1000 to 300,000, still more preferably 3000. Polymerization may be performed so that the amount becomes ˜100,000. In addition, the preferable carbon number of R 'is the same as the preferable carbon number of said R.

The terminal of the polyester unit obtained by the reaction of the compound (X) having the g value of the general formula (1) and the h value of 1 of the general formula (2) with the polyhydric alcohol (Y) is a carboxyl group or a hydroxyl group And is represented by the following general formula (6):

(Wherein R ¹ represents a hydrocarbon group having 2 to 300 carbon atoms, R ² represents a hydrocarbon group having 2 to 500 carbon atoms which may contain an oxygen atom or a nitrogen atom, and m represents an average degree of polymerization) X represents a number of 1 or more, preferably 5 to 500, X represents either HO— or HO—R ² —O—, and Y represents either a hydrogen atom or —CO—R ¹ —COOH. Represents)
Furthermore, you may make another compound react with the compound represented by General formula (6). However, when other compounds are reacted, the proportion of the polyester, which is a reaction product obtained by the reaction between the compound (X) and the polyhydric alcohol (Y), is 50% by mass of the total molecular weight (weight average molecular weight). It should be above, preferably 70% by mass or more, more preferably 90% by mass or more, and most preferably not react with other compounds. In addition, when the ratio of polyester will be less than 50 mass%, the performance as a low-temperature fluidity improver cannot be exhibited.

The terminal of the polyester unit obtained by the reaction of the compound (X) having a g value of the general formula (1) or a h value of 2 to 1000 of the general formula (2) with the polyhydric alcohol (Y) is a carboxyl group And a hydroxyl group, represented by the following general formula (7):

(Wherein R ¹ represents a hydrocarbon group having 2 to 300 carbon atoms, R ² represents a hydrocarbon group having 2 to 500 carbon atoms which may contain an oxygen atom or a nitrogen atom, and m represents an average degree of polymerization) 1 represents a number of 1 or more, preferably 5 to 500, 1 represents an average degree of polymerization, represents a number of 2 to 1000, and X represents either HO— or HO—R ² —O—. Y represents a hydrogen atom or —CO—R ¹ H ₂ —COOH)
Furthermore, you may make another compound react with the compound represented by General formula (7). However, when other compounds are reacted, the proportion of the polyester obtained by the reaction between the compound (X) and the polyhydric alcohol (Y) must be 50% by mass or more of the total molecular weight (weight average molecular weight). However, it is preferably 70% by mass or more, more preferably 90% by mass or more, and most preferably one that does not react with other compounds. In addition, when the ratio of polyester will be less than 50 mass%, the performance as a low-temperature fluidity improver cannot be exhibited.

The other compound that can be reacted may be any compound that reacts with a hydroxyl group or a carboxylic acid, but is preferably a compound that does not generate an ionic group after the reaction, for example, alcohol, fatty acid, amine Etc.

Examples of the alcohol include the polyhydric alcohols listed above, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, isopentanol, secondary pentanol, neopentanol, Tertiary pentanol, hexanol, secondary hexanol, heptanol, secondary heptanol, octanol, 2-ethylhexanol, secondary octanol, nonanol, secondary nonanol, decanol, secondary decanol, undecanol, secondary undecanol, dodecanol, secondary Dodecanol, tridecanol, isotridecanol, secondary tridecanol, tetradecanol, secondary tetradecanol, hexadecanol, secondary hexadecanol, stearyl alcohol Isostearyl alcohol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, myricyl alcohol, lasserol, tetratriacontanol, 2-butyloctanol, 2-butyldecanol, 2-hexyloctanol, 2-hexyldecanol, 2-octyl decanol, 2-hexyl decanol, 2-octyl decanol, 2-decyl tetradecanol, 2-dodecyl hexadecanol, 2-hexadecyl octadecanol, 2-tetradecyl octadecanol, cyclopen Examples thereof include monohydric alcohols such as butanol, cyclohexanol, cycloheptanol, methylcyclopentanol, methylcyclohexanol, methylcycloheptanol, and benzyl alcohol. The alcohol reacts with the carboxylic acid at the end of the polyester to form an ester bond.

Examples of fatty acids include acetic acid, propionic acid, butanoic acid (butyric acid), pentanoic acid (valeric acid), isopentanoic acid (isovaleric acid), hexanoic acid (caproic acid), heptanoic acid, isoheptanoic acid, octanoic acid (caprylic acid) ), 2-ethylhexanoic acid, isooctanoic acid, nonanoic acid (pelargonic acid), isononanoic acid, decanoic acid (capric acid), isodecanoic acid, undecanoic acid, isoundecanoic acid, dodecanoic acid (lauric acid), isododecanoic acid, tridecanoic acid , Isotridecanoic acid, tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), isostearic acid, eicosanoic acid (arachinic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosane Acid (serotic acid), octacosanoic acid (molybdate) Tan acid), 10-undecenoic acid, Zomarin acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, gadoleic acid, erucic acid, selacholeic acid, mixed fatty acids obtained from natural oils and fats and the like. The fatty acid reacts with the hydroxyl group at the end of the polyester to form an ester bond.

Examples of amines include primary amines and secondary amines. Examples of primary amines include methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, pentylamine, isopentylamine, hexylamine, and isohexyl. Amine, octylamine, 2-ethylhexylamine, nonylamine, isononylamine, decylamine, isodecylamine, undecylamine, isoundecylamine, dodecylamine, isododecylamine, tridecylamine, isotridecylamine, tetradecylamine , Isotetradecylamine, hexadecylamine, isohexadecylamine, octadecylamine, isooctadecylamine, oleylamine and the like. Secondary amines include, for example, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, dipentylamine, diisopentylamine, dihexylamine, diisohexylamine, dioctylamine, di-2- Ethylhexylamine, dinonylamine, diisononylamine, didecylamine, diisodecylamine, diundecylamine, diisoundecylamine, didodecylamine, diisododecylamine, ditridecylamine, diisotridecylamine, ditetradecylamine, diisotetradecylamine , Dihexadecylamine, diisohexadecylamine, dioctadecylamine, diisooctadecylamine, dioleylamine and the like. The amine reacts with the carboxyl group at the end of the polyester to form an amide bond.

The predicate “biodiesel fuel” described in the present specification is a fuel containing 100 mass% fatty acid methyl ester or light oil and fatty acid methyl ester, and the light oil is No. 1 light oil standardized in JIS K2204. Any general diesel oil that can be used in diesel engines such as No. 2, No. 2 diesel oil and No. 3 diesel oil can be used.

Fatty acid methyl esters include those made from natural fats and oils obtained from plants, those made from natural fats and oils obtained from animals such as pork fat and beef tallow, and those made from these waste cooking oils. Any can be used. Examples of plant-based natural fats and oils include, for example, Jatropha oil, sand peach oil, flower bud oil, flaxseed oil, eno oil, oil deer oil, olive oil, cacao fat, kapok oil, white mustard oil, sesame oil, rice bran oil, safflower oil, Shea nut oil, cinnamon oil, soybean oil, tea seed oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, castor oil, sunflower oil, cottonseed oil, coconut oil, tree wax, peanut oil, and mixtures thereof Is mentioned. The fatty acid methyl ester may be produced by any known method, for example, by heating the above natural oil and methanol under an alkali catalyst such as sodium hydroxide or potassium hydroxide. Examples include a method obtained by transesterification to remove glycerin that is produced as an impurity.

When blending light oil and fatty acid methyl ester, it is preferable to blend so that fatty acid methyl ester is 2% by mass or more based on the total amount of biodiesel fuel. If the fatty acid methyl ester is less than 2% by mass, it is insufficient to achieve the original purpose of biodiesel fuel, which is to reduce the amount of fossil fuel used and reduce carbon dioxide emissions. This is not preferable because the significance is lost.

The biodiesel fuel composition of the present invention comprises the above biodiesel fuel and the low temperature fluidity improver of the present invention. The blending amount of the low temperature fluidity improver of the present invention with respect to the biodiesel fuel is not particularly limited, but it is preferably blended by 0.001 to 5% by mass with respect to the total amount of the biodiesel fuel, and 0.005 to 3 The mass% is more preferable. If the blending amount is less than 0.001% by mass, a sufficient effect may not be exhibited. If the blending amount exceeds 5% by mass, an effect corresponding to the blending amount may not be obtained, or an insoluble material may be generated depending on the type of fuel. It is not preferable because it may.

The biodiesel fuel composition of the present invention can be mixed with a cetane number improver as necessary. As the cetane number improver, various compounds known as light oil cetane number improvers can be arbitrarily used. For example, 2-chloroethyl nitrate, 2-ethoxyethyl nitrate, isopropyl nitrate, butylnite. Rate, primary amyl nitrate, secondary amyl nitrate, isoamyl nitrate, primary hexyl nitrate, secondary hexyl nitrate, n-heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate, cyclohexyl night Examples thereof include ethylene glycol dinitrate, and alkyl nitrates having 6 to 8 carbon atoms are particularly preferable. The content of the cetane number improver is in the range of 500 to 1400 ppm by mass, preferably 600 to 1250 ppm by mass, more preferably 700 to 1100 ppm by mass with respect to the total amount of the biodiesel fuel composition. When the cetane number improver is blended, if the blending amount is less than 500 ppm by mass, a sufficient cetane number improving effect cannot be obtained, and particulate matter (PM), aldehydes in diesel engine exhaust gas, and further It is not preferable because NOx may not be sufficiently reduced. Moreover, even if the compounding quantity of a cetane number improver exceeds 1400 mass ppm, since the effect corresponding to it cannot be expected and it becomes economically disadvantageous, it is unpreferable.

Moreover, a detergent can be blended in the biodiesel fuel composition of the present invention as necessary. Examples of the detergent include imide compounds; alkenyl succinimides such as polybutenyl succinimides synthesized from polybutenyl succinic anhydrides and ethylene polyamines; polyhydric alcohols such as pentaerythritol and polybutyls. Succinic acid esters such as polybutenyl succinic acid ester synthesized from tenyl succinic anhydride; copolymer polymers such as dialkylaminoethyl methacrylate, polyethylene glycol methacrylate, vinyl pyrrolidone and alkyl methacrylate copolymers, carboxylic acids and amines Ashless detergents such as reaction products of alkenyl succinic acid imide and reaction products of carboxylic acid and amine are preferred. These detergents can be used alone or in combination of two or more. The blending amount of the detergent is not particularly limited, but in order to bring out the effect of blending the detergent, specifically, the effect of suppressing clogging of the fuel injection nozzle, the blending amount of the detergent is the biodiesel fuel composition. It is within the range of 30 to 300 ppm by mass, preferably 60 to 200 ppm by mass relative to the total amount of the product. When the blending amount of the detergent is less than 30 ppm by mass, the above-mentioned effect may not appear, and even if it exceeds 300 ppm by mass, an effect commensurate with it cannot be expected. Conversely, NOx in diesel engine exhaust gas , PM, aldehydes and the like may be increased, which is not preferable.

Furthermore, other known fuel oil additives can be added to the biodiesel fuel composition of the present invention alone or in combination of several kinds for the purpose of further enhancing the performance. Examples of other additives include solvents such as methanol, ethanol, propanol, butanol, hexane, toluene, dimethylbenzene, and trimethylbenzene; antioxidants such as phenols, amines, and vitamins; fatty acids, glycerin esters, and alkyls. Lubricants such as amines and fatty acid amides; metal deactivators such as salicylidene derivatives; anti-icing agents such as polyglycol ethers; corrosion inhibitors such as aliphatic amines and alkenyl succinic acid esters; anionic and cationic Antistatic agents such as amphoteric surfactants; colorants such as azo dyes; and silicon-based antifoaming agents. The blending amount of other additives can be arbitrarily determined, but the blending amount of each additive is 0.001 to 0.5% by mass, more preferably 0.001 based on the total amount of the biodiesel fuel composition. Within the range of 0.2 mass%.

Hereinafter, the present invention will be specifically described by way of examples. In the following examples and the like, “%” and “ppm” are based on mass unless otherwise specified.

(A-1) Polyester obtained from 1 mol of octadecylidene succinic anhydride and 1 mol of ethylene glycol (weight average molecular weight = 5000) [In the general formula (6), the carbon number of R ¹ = 20, the carbon number of R ² = 2 X = HO— and HO—R ² —O—, Y = hydrogen atom and —CO—R ¹ —COOH, average degree of polymerization m = 12.2]
(A-2) Polyester obtained from 1 mol of octadecylidene succinic anhydride and 1 mol of diethylene glycol (weight average molecular weight = 5200) [In the general formula (6), the carbon number of R ¹ = 20, the carbon number of R ² = 4, X = HO— and HO—R ² —O—, Y = hydrogen atom and —CO—R ¹ —COOH, average degree of polymerization m = 11.5]
(A-3) Polyester (weight average molecular weight = 9800) obtained from 1 mol of octadecylidene succinic anhydride and 1 mol of polyethylene glycol (weight average molecular weight 800, average carbon number 36) [in the general formula (6), carbon of R ¹ Number = 20, R ² carbon number = 36, X = HO— and HO—R ² —O—, Y = hydrogen atom and —CO—R ¹ —COOH, average degree of polymerization m = 8.5]
(A-4) Polyester obtained from 1 mol of hexadecylidene succinic anhydride and 1 mol of glycerin (weight average molecular weight = 8000)
(A-5) Polyester obtained from 1 mol of octadecylidene succinic anhydride and 1 mol of 1,6-hexanediol (weight average molecular weight = 6000) [in the general formula (6), the carbon number of R ¹ = 20, R ² Carbon number = 6, X = HO— and HO—R ² —O—, Y = hydrogen atom and —CO—R ¹ —COOH, average degree of polymerization m = 12.9]
(A-6) Polyester obtained from 1 mol of octadecylidene succinic acid and 1 mol of ethylene glycol (weight average molecular weight = 5000) [in the general formula (6), the carbon number of R ¹ = 20, the carbon number of R ² = 2, X = HO— and HO—R ² —O—, Y = hydrogen atom and —CO—R ¹ —COOH, average degree of polymerization m = 12.2]
(A-7) Polyester obtained from 1 mol of alkenyl succinic acid and 1 mol of ethylene glycol (alkenyl group is a polybutenyl group having an average carbon number of 71) (weight average molecular weight = 10300) [in the general formula (6), the carbon number of R ¹ = 73, R ² carbon number = 2, X = HO— and HO—R ² —O—, Y = hydrogen atom and —CO—R ¹ —COOH, average degree of polymerization m = 8.9]
(A-8) Polyester obtained from 1 mol of succinic acid and 1 mol of ethylene glycol (weight average molecular weight = 4200) [in the general formula (6), R ¹ carbon number = 2, R ² carbon number = 2, X = HO — And HO—R ² —O—, Y = hydrogen atom and —CO—R ¹ —COOH, average degree of polymerization m = 29.2]
(A-9) Polyester obtained from 1 mol of octadecylidene succinic anhydride and 0.7 mol of ethylene glycol (weight average molecular weight = 4700) [in general formula (6), carbon number of R ¹ = 20, carbon number of R ² = 2, X = HO— and HO—R ² —O—, Y = hydrogen atom and —CO—R ¹ —COOH, average degree of polymerization m = 11.5]
(A-10) Polymer obtained by reacting 0.1 mol of laurylamine with the polyester obtained in a-9 (weight average molecular weight = 4900; ratio of polyester = 95% by mass)
(A-11) Polyester obtained from 1 mol of octadecylidene succinic anhydride and 0.5 mol of ethylene glycol (weight average molecular weight = 3000) [in general formula (6), carbon number of R ¹ = 20, carbon number of R ² = 2, X = HO— and HO—R ² —O—, Y = hydrogen atom and —CO—R ¹ —COOH, average degree of polymerization m = 7.3]
(A-12) Polyester obtained from 1 mol of octadecylidene succinic anhydride and 0.5 mol of diethylene glycol (weight average molecular weight = 3800) [In the general formula (6), the carbon number of R ¹ = 20, the carbon number of R ² = 4, X = HO— and HO—R ² —O—, Y = hydrogen atom and —CO—R ¹ —COOH, average degree of polymerization m = 8.4]
(A-13) Polymer obtained from 1 mol of octadecene and 1 mol of maleic anhydride [in general formula (2), average polymerization degree h = 30, carbon number of A = 20], polyester obtained from 0.5 mol of ethylene glycol (weight) (Average molecular weight = 220600) [In the general formula (7), the carbon number of R ¹ = 20, the carbon number of R ² = 2, X = HO— and HO—R ² —O—, Y = hydrogen atom and —CO— R ¹ —COOH, average polymerization degree l = 30, average polymerization degree m = 18.5]
(A-14) A mixture of 75% by mass of the compound (a-1) and 25% by mass of the compound (a-13).

(B-1) Ester compound obtained from 1 mol of dodecanoic acid and 0.5 mol of polyethylene glycol (polyethylene glycol is the same as that used in a-3) (weight average molecular weight = 1000)
(B-2) Polyester obtained from 1 mol of malonic acid and 1 mol of ethylene glycol (weight average molecular weight = 4900) [in the general formula (6), R ¹ carbon number = 1, R ² carbon number = 2, X = HO — And HO—R ² —O—, Y = hydrogen atom and —CO—R ¹ —COOH, average degree of polymerization m = 37.7]
(B-3) Ester compound obtained from 1 mol of octadecanoic acid and 1 mol of triethylene glycol (weight average molecular weight = 500)
(B-4) Ester compound obtained from 1 mol of octadecylidene succinic anhydride and 2 mol of hexadecanol (weight average molecular weight = 500)
(B-5) Polyester obtained from 1 mol of alkenyl succinic acid and 1 mol of ethylene glycol (alkenyl group is a polybutenyl group having an average carbon number of 350) (weight average molecular weight = 28000) [in the general formula (6), the carbon number of R ¹ = 352, R ² carbon number = 2, X = HO— and HO—R ² —O—, Y = hydrogen atom and —CO—R ¹ —COOH, average degree of polymerization m = 5.5]

The polyester (a-1) was synthesized by the following method.
A 1000 ml flask equipped with a nitrogen inlet tube, a reflux tube, a nitrogen blowing tube equipped with a stirrer and a thermometer and a condenser was charged with 1 mol (252 g) of octadecene and 1 mol (98 g) of maleic anhydride and heated to 210 ° C. The reaction was carried out at a temperature for 20 hours to obtain 350 g of octadecylidene succinic anhydride. Subsequently, after cooling to 80 ° C., 1 mol (62 g) of ethylene glycol was added, the pressure was reduced to 1.3 kPa, the temperature was raised to 160 ° C., and the reaction was carried out for 2 hours to obtain the polyester (a-1). It was.

For (a-2) to (a-5), (a-9), (a-11), (a-12), and (b-4), an esterification reaction was performed in the same manner as described above. For the polymer of (a-10), 0.1 mol (18.5 g) of laurylamine was added to (a-9) after completion of the reaction, and an amidation reaction was carried out at 180 ° C. for 3 hours to obtain ( Laurylamine was reacted with the polyester terminal of a-9).

The polyester (a-6) was synthesized by the following method.
A 10000 ml flask equipped with a nitrogen inlet tube, reflux tube, stirring device and thermometer and a condenser was charged with 1 mol (252 g) of octadecene and 1 mol (98 g) of maleic anhydride and heated to 210 ° C. The reaction was carried out at temperature for 20 hours. Subsequently, the mixture was cooled to 80 ° C., charged with 2 mol (36 g) of water, reacted at 100 ° C. for 3 hours for hydrolysis, and then dehydrated under reduced pressure to obtain 386 g of octadecylidene succinic acid. Subsequently, 1 mol (62 g) of ethylene glycol was added, the pressure was reduced to 1.3 kPa, and the reaction was performed at 160 ° C. for 4 hours to obtain the polyester (a-6).

For (a-7) and (a-8), polyester was obtained in the same manner as above. For (b-1) to (b-3) and (b-5), an esterification reaction was performed in the same manner as the above esterification reaction.

The polyester (a-13) was synthesized by the following method.
A 1000 ml flask equipped with a nitrogen inlet tube, a reflux tube, a stirrer and a thermometer and a condenser was added to 1 mol (252 g) of octadecene and 1 mol (98 g) of maleic anhydride, and azobisisobutyronitrile 3 as a catalyst. 0.5 g was charged, heated to 220 ° C., and reacted at the same temperature for 20 hours to obtain a polymer of octadecene and maleic anhydride [in the general formula (2), the number of carbons of A = 20, average polymerization degree h = 30 ]. Subsequently, after cooling to 80 ° C. and adding 0.5 mol (31 g) of ethylene glycol, the pressure was reduced to 1.3 kPa, the temperature was raised to 160 ° C., and the reaction was conducted for 2 hours to obtain the polyester of (a-13) Got.

<Measurement method of weight average molecular weight>
The weight average molecular weight was calculated by GPC. The equipment and measurement conditions used for the measurement are as follows.
Detector: RI detector HLC-8120GPC [Tosoh Corporation]
Column: TSKgel G4000Hxl, TSKgel G3000Hxl, TSKgel G2000Hxl [both Tosoh Corp.] connected in series Developing solvent: THF (tetrahydrofuran)
Developing solvent flow rate: 1 ml / min Sample concentration: 0.5% by mass
Measurement temperature: 40 ° C

<Pour point test>
Biodiesel using the base oil 1 (100% soybean oil-derived fatty acid methyl ester) or base oil 2 (light oil containing 30% soybean oil-derived fatty acid methyl ester) with the low-temperature fluidity improver shown in Table 1 The fuel composition was prepared and measured by the method described in JIS K2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”. That is, a 45 ml sample (biodiesel fuel composition) is placed in a test tube and heated to 45 ° C., and then the sample is cooled using a cooling bath. Each time the temperature of the sample drops 2.5 ° C, the test tube is removed from the cooling bath and tilted. The temperature when the sample stops moving for 5 seconds is read, and the value obtained by adding 2.5 ° C to this value is the pour point. It was. The light oil used in the experiment was equivalent to No. 1 light oil standardized in JIS K2204.

From Table 1, it can be seen that the biodiesel fuel composition using the low-temperature fluidity improver of the present invention has a lower pour point for both base oil 1 and base oil 2 and an improved low-temperature fluidity. .

The low temperature fluidity improver for biodiesel fuel of the present invention can be suitably used for improving the low temperature fluidity of a biodiesel fuel containing a fatty acid methyl ester.

Claims

Compound (X) represented by the following general formula (1) and / or general formula (2),

(In the formula, AH 2 represents a hydrocarbon group having 2 to 300 carbon atoms, g represents an average degree of polymerization, and represents a number of 1 to 1000.)

(In the formula, AH 2 represents a hydrocarbon group having 2 to 300 carbon atoms, h represents an average degree of polymerization, and represents a number of 1 to 1000.)
One or more polyhydric alcohols (Y) represented by the following general formula (3)
R- (OH) n (3)
(In the formula, R represents a hydrocarbon group having 2 to 500 carbon atoms which may contain an oxygen atom or a nitrogen atom, and n represents a number of 2 or more.)
A low-temperature fluidity improver for biodiesel fuel, which is a polymer containing 50% by mass or more of polyester, which is a reaction product of
The low-temperature fluidity improver for biodiesel fuel according to claim 1, wherein the compound (X) is alkenyl succinic acid, alkenyl succinic anhydride, or polymaleic acid derivative.
The bio of claim 1 or 2, wherein when g of the general formula (1) is 1 or h of the general formula (2) is 1, the polyester has a polyester unit represented by the following general formula (4). Low temperature fluidity improver for diesel fuel:

(In the formula, A represents a hydrocarbon group having 2 to 300 carbon atoms, and R ′ represents a hydrocarbon group having 2 to 500 carbon atoms which may contain an oxygen atom or a nitrogen atom.)
When g in the general formula (1) is 2 to 1000 or h in the general formula (2) is 2 to 1000, the polyester has a polyester unit represented by the following general formula (6). 2. Low temperature fluidity improver for biodiesel fuel according to 2:

(In the formula, A represents a hydrocarbon group having 2 to 300 carbon atoms, and R ′ represents a hydrocarbon group having 2 to 500 carbon atoms which may contain an oxygen atom or a nitrogen atom.)
Compound (X) represented by the following general formula (1) and / or general formula (2),

(In the formula, AH 2 represents a hydrocarbon group having 2 to 300 carbon atoms, and g represents a number of 1 to 1000.)

(In the formula, AH 2 represents a hydrocarbon group having 2 to 300 carbon atoms, and h represents a number of 1 to 1000.)
One or more polyhydric alcohols (Y) represented by the following general formula (3)
R- (OH) n (3)
(In the formula, R represents a hydrocarbon group having 2 to 500 carbon atoms which may contain an oxygen atom or a nitrogen atom, and n represents a number of 2 or more.)
A low-temperature fluidity improver for biodiesel fuel, characterized in that the polyester is a reaction product of
A biodiesel fuel composition comprising the biodiesel fuel low-temperature fluidity improver according to any one of claims 1 to 5 and biodiesel fuel.
The biodiesel fuel composition according to claim 6, further comprising a cetane number improver and / or a detergent.
Further, one or more selected from the group consisting of a solvent, an antioxidant, a lubricity improver, a metal deactivator, an anti-icing agent, a corrosion inhibitor, an antistatic agent, a colorant and an antifoaming agent. The biodiesel fuel composition according to claim 6 or 7, comprising other additives.