JPH0334790B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a flowability improving additive for fuel oil. In recent years, in the case of fuel oil, especially light oil, in order to meet the strong demand for kerosene, the proportion of low boiling point parts has been decreasing, forcing the boiling point range to be narrowed. By narrowing the boiling point range of light oil in this way, the carbon chain distribution of n-paraffin contained therein becomes narrower, making it suitable for most fluidity improving additives, including the widely used ethylene-vinyl acetate system. However, in many cases, it is impossible to reduce the clogging temperature of the fuel filters of internal combustion engines, which are the major applications of these fuel oils, at low temperatures. Some measures have already been taken to solve this problem. However, so far, for fuel oils with such a narrow boiling point range, flow-improving additives that can lower the CFPP (cold filter plugging point, IP306) and simultaneously have the ability to lower the pour point have been developed. No agent has been found. The present inventors have conducted extensive research in order to develop a fluidity-improving additive that exhibits excellent CFPP lowering ability for fuel oils with narrow boiling point ranges and also has a certain degree of pour point (PP) lowering ability. As a result, the present invention was achieved. That is, the present invention provides a polyoxyalkylene ether of a polyhydric alcohol having at least 4 hydroxyl groups and an equivalent weight of 85 to 1500, and a carbon number
Complete esters with 14-30 straight chain saturated fatty acids and optionally other carboxylic acids; and optionally (B)
Selected from the group consisting of nitrogen-containing derivatives of alkenylsuccinic acids, condensates of chlorinated paraffins and naphthalene, nitrogen-containing derivatives of long-chain alkylene dicarboxylic acids, nitrogen-containing derivatives of tricarboxylic acids, and reaction products of diisocyanate compounds and dialkylamines. A fluidity improving additive for fuel oil characterized by containing a compound. Component (A) of the fluidity improving additive of the present invention (hereinafter also referred to as the additive of the present invention) is a polyoxyalkylene ether of a polyhydric alcohol having an equivalent weight of at least 4 hydroxyl groups and 85 to 1500 carbon atoms.
As a complete ester with a carboxylic acid that essentially contains 14 to 30 linear saturated fatty acids, the general formula is [In the formula, R is a residue of a polyhydric alcohol; A is an alkylene group having 2 to 4 carbon atoms; R' is a carboxylic acid residue, and at least one of the m R's has a carbon number of 14
~30 straight chain saturated fatty acid residues. m is an integer of 4 or more, n is R[-(OA) _o OH] the equivalent of _n is 85 ~
The number is 1500. ] Examples include compounds represented by: In the general formula (1), the polyhydric alcohol having 4 or more hydroxyl groups forming the residue R has the general formula R(OH) _n (2) (where m is an integer of 4 or more, and R is (It is an m-valent hydrocarbon group that may contain one or more ether oxygen atoms or thioether sulfur atoms.)
Examples include compounds shown in Examples of such polyhydric alcohols include 4-
octavalent alkane polyol, saccharide, saccharide derivative,
Examples include polyalkane polyols and mixtures of two or more thereof. Examples of the above-mentioned alkane polyols include pentaerythritol and butanetetraol; examples of sugars include sucrose; examples of sugar derivatives include sugar alcohols such as sorbitol and mannitol; examples of polyalkane polyols include condensation products of alkane polyols (glycerin, pentaerythritol, etc.) (degree of polymerization is 2 to 10 or higher), such as polyglycerin (degree of polymerization 3 to 10), di- or tripentaerythritol, and has 5 to 8 hydroxyl groups as described in U.S. Pat. No. 4,233,170. Polyhydric alcohols can also be used. Among these, preferred are 4 to 8 alkane polyols, saccharides and saccharide derivatives,
Particularly preferred are pentaerythritol, sorbitan, sorbitol and moss. Examples of the alkylene group having 2-4 carbon atoms in A include ethylene, propylene, butylene (1,2-;2,
3-; 1,3- and 1,4-) groups. These may be two or more types (random and/or block). Preferred among these are ethylene and/or propylene groups. n is a number such that the equivalent weight of the polyoxyalkylene ether represented by the formula R[-(OA) _o OH] _n is 85 to 1500, preferably 100 to 500 (m n's may be the same or different) ). When the equivalent weight of the polyoxyalkylene ether is less than 85,
Generally, solubility in fuel oil is good, but
CFPP lowering ability is not sufficient. Furthermore, if the equivalent weight exceeds 1500, the solubility in fuel oil is insufficient, or even if the solubility is maintained, the ability to lower CEPP is insufficient. In the range of equivalent weight from 100 to 500, it exhibits excellent CFPP lowering ability and also has PP lowering ability, while also maintaining good solubility in fuel oil. In general formula (1), at least one of m R′
The fatty acids that form the residue of linear saturated fatty acids with 14 to 30 carbon atoms include myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid,
Examples include lignoceric acid, cerotic acid, montanic acid, melisic acid, and preferred ones are palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid. These may be used alone or in combination of two or more. For example, a mixed fatty acid obtained by hydrogenating a fatty acid obtained by hydrolyzing a natural oil such as beef tallow can also be used as it is. In general formula (1), the number of carbon atoms among m R′ is 14 to
30 aliphatic linear saturated carboxylic acid residues at least 1
If it is not included, the effect of reducing CFPP and PP will be small. Other carboxylic acids forming the carboxylic acid residue of R' include carboxylic acids having 1 to 30 carbon atoms, such as straight chain saturated fatty acids having 1 to 13 carbon atoms (acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, pelargonic acid, acids, lauric acid, etc.), unsaturated fatty acids with 3 to 30 carbon atoms (oleic acid, linoleic acid, linolenic acid, etc.), oxyacids with 2 to 30 carbon atoms (glycolic acid,
ricinoleic acid, etc.), branched fatty acids having 4 to 30 carbon atoms (2-ethylhexanoic acid, isostearic acid, etc.), aromatic carboxylic acids (benzoic acid, naphthalene carboxylic acid, etc.), and mixtures of two or more of these. Among these, preferred are the above-mentioned straight chain saturated fatty acids and unsaturated fatty acids. The compound represented by general formula (1) must be a complete ester. When this compound is a partial ester, the effect of lowering CFPP and PP is small. In addition, in the present invention, as component (A), the general formula
In place of or in addition to those shown in (1), polycarboxylic acids such as adipic acid, sebacic acid, dodecanedicarboxylic acid, butanetricarboxylic acid may be used as part of the carboxylic acid to the extent that the solubility in fuel oil does not deteriorate. (usually 25 mol% or less in the carboxylic acid component) may be used in combination. Such esters include, for example, the general formula [In the formula, R″ is a polycarboxylic acid residue; p is 2, 3,
...(Basicity of polycarboxylic acid); R, R', A, n
is the same as in general formula (1). ] Examples include compounds containing the following compounds. Component (A) can be produced by various methods. For example, first, the polyhydric alcohol is dissolved as it is or in a suitable solvent that is inert to the reaction system,
Generally, a catalyst such as a caustic alkali is added, and an alkylene oxide having 2 to 4 carbon atoms (ethylene oxide, propylene oxide, butylene oxide, etc.) is added in a liquid or gaseous state under heating and reacted. 2
When more than one type of alkylene oxide is reacted, random addition polymerization may be used, in which two or more alkylene oxides are mixed and reacted, or one type of alkylene oxide may be reacted first, and then other alkylene oxides may be sequentially added. Block addition polymerization may also be carried out. The thus obtained polyoxyalkylene ether may be used as it is or after being purified to remove unreacted substances or catalysts, and then esterified with a carboxylic acid and usually a catalyst such as sulfuric acid under heating. In esterification, the equivalent ratio of the hydroxyl group of the polyoxyalkylene ether to the carboxyl group of all the carboxylic acids is preferably around 1:1. Also,
The linear saturated fatty acid having 14 to 30 carbon atoms is used in an amount of 1 mol or more, preferably 2 to mmol, per 1 mol of polyoxyalkylene ether. When esterifying, first esterify with a straight chain saturated fatty acid having 14 to 30 carbon atoms, and then esterify with another carboxylic acid. The esterification reaction may be carried out again by adding a saturated fatty acid, or may be carried out using a mixture containing a linear saturated fatty acid having 14 to 30 carbon atoms and another carboxylic acid.
Progress of the reaction can be confirmed by monitoring acid value, hydroxyl value, saponification value, etc. Although the component (A) thus obtained may contain a small amount of unreacted substances, it can usually be used without any problem even if it is not removed. The state of component (A) in the present invention varies depending on the type of polyhydric alcohol, alkylene oxide and carboxylic acid used, the molecular weight of the polyether polyol, etc., but it is usually in a viscous liquid or solid state, and is usually a petroleum-based solvent, Although it is soluble in solvents such as alcohols and esters, it is insoluble in water, although it may be dispersed. Component (A) in the present invention is a combination of a polyoxyalkylene ether of an alkantriol (the average molecular weight of the ether is 250 to 6,000), a straight chain saturated fatty acid having 14 to 30 carbon atoms, and, if necessary, another carboxylic acid. Can be used in combination with complete esters. Examples of such esters include those described in the specification of a patent application filed on December 12, 1982 by the present applicant (title of the invention: ``Fuel Oil Flow Improving Additive''). The ratio when used together is not particularly limited, but the weight ratio is, for example, 99:1 to 1:99. In the present invention, if necessary, component (B) may include a nitrogen-containing derivative of alkenylsuccinic acid, a condensate of chlorinated paraffin and naphthalene, a nitrogen-containing derivative of long-chain alkylene dicarboxylic acid, a nitrogen-containing derivative of long-chain alkylene dicarboxylic acid, One or more of the nitrogen-containing derivatives of tricarboxylic acids, the reaction products of diisocyanate compounds and dialkylamines (urea and/or Biuret derivatives) as described above.
Can be used in combination with (A). The combined use of component (B) has the great effect of promoting PP lowering ability. Additionally, ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, chlorinated paraffins, and (meth)acrylic acid copolymers containing long-chain alkyl groups are also used as fluidity-improving additives for fuel oil. However, when component (A) in the present invention and these polymeric fluidity improvers were used together, no effect of promoting PP lowering ability was observed, and
This is not preferable because it reduces the ability to lower CFPP. As the nitrogen-containing derivative of alkenylsuccinic acid as component (B), alkenylsuccinic acid containing a C ₄ to _{C 28} alkenyl group, mono- or dialkylamine, (poly)
Examples include reactants (amides and/or salts) with alkylene polyamines, and preferred ones are C ₁₄
It is a reaction product of an alkenylsuccinic acid containing a ~ _C22 alkenyl group and a dialkylamine having two _C14 ~ _C20 alkyl groups. Examples of condensates of chlorinated paraffins and naphthalene include condensates of chlorinated paraffins of C ₈ or more and naphthalene. Its molecular weight is usually
It ranges from 2000 to 8000. Examples of the nitrogen-containing derivatives of long-chain alkylene carboxylic acids include those described in JP-A-56-36588. Specifically, it is a reaction product of a dicarboxylic acid having an unsubstituted or alkyl-substituted alkylene group having a C ₁₀ or more linear alkylene chain and a dialkylamine, preferably a dicarboxylic acid having a C ₁₄ to ₂₂ linear alkylene group. _and C _14-22 alkyl group 2
It is a reaction product with a dialkylamine having . As a nitrogen-containing derivative of tricarboxylic acid, JP-A-Sho
56-84795, specifically, it is a reaction product of an aromatic, aliphatic or alicyclic tricarboxylic acid and a dialkylamine, preferably a reaction product of trimellitic acid and a C ₁₄ to _{C 22} tricarboxylic acid. It is a reaction product with a dialkylamine having two alkyl groups. In addition, as a reaction product of a polyisocyanate compound and a dialkylamine, JP-A-56-93796
Examples include those described in the publication No. Specifically, it is a reaction product of an aromatic, aliphatic, or alicyclic polyisocyanate and a dialkylamine, and preferably a reaction product of tolylene diisocyanate and a dialkylamine having two C ₁₄ to ₂₂ alkyl groups. The above (B) can be used alone or in combination with (A) as a mixture. Among (B), preferred are nitrogen-containing derivatives of alkenylsuccinic acid. When (A) and (B) are used together, their usage ratio can be set arbitrarily, but the preferred range is (A):(B) = 2:98 to 98:2 in terms of weight ratio. The fuel oil in the present invention is mainly a distillate fuel oil and a fuel oil in which a distillate fuel oil is mixed with a residual oil, and specific examples include gasoline, kerosene, light oil, and heavy oil (A heavy oil, B heavy oil). Among these, preferred are kerosene, light oil and A heavy oil. When adding the additive of the present invention to fuel oil, the amount added is usually 0.0001 to 0.5% (the same below weight), preferably 0.001 to 0.1%. The method of adding the additive of the present invention to fuel is not particularly limited. In the case of additives consisting of (A) and (B), for example, (A) and (B) may be mixed in advance and added to fuel oil, or (A) and (B) may be added separately to fuel oil. However, there is a method of forming an additive consisting of (A) and (B) in fuel oil. When mixing in advance, use (A) and
Examples include a method of heating and uniformly mixing (B) and a method of dissolving at least one of (A) and (B) in a solvent and then mixing. In addition, as a method for forming additives in the above fuel oil, (A) and (B) may be added as they are, or at least one of (A) and (B) may be dissolved in a solvent and both may be added simultaneously or sequentially to the fuel oil. One method is to add it. The additive of the present invention is a fluidity improving additive of a copolymer system such as ethylene-vinyl acetate copolymer, and a fluidity improving additive of a condensation system such as a chlorinated paraffin-naphthalene condensate. Fuel oils with a very narrow boiling point range and n-
In addition to exhibiting excellent CFPP lowering ability with very low addition amount to fuel oil with high paraffin content,
Excellent for fuel oils with a relatively wide boiling point range, where flowability improving additives have traditionally been effective.
Shows CFPP lowering ability. Also, PP along with CFPP descending ability
It also has the ability to descend. In particular, by using component (B) in combination, a fluidity improver having excellent CFPP lowering ability and PP lowering ability can be provided. Until now, there have been no examples of using compounds with polyether bonds in the molecule as additives for fuel oil; for example, compounds with OH groups remaining, such as polyethylene glycol monostearate and polyoxyethylene sorbitan triolate. However, these alone do not have sufficient fluidity improvement effects;
It is said to be effective only when used in combination with ethylene polymers, halogenated ethylene polymers, ethylene and monocarboxylic acid vinyl ester copolymers, ethylene and (meth)acrylate ester copolymers, etc. . Also

Diesters of polyoxyalkylene glycols as shown by the formula [formula] also exhibit a certain degree of CFPP lowering ability for distillate fuel oils having a narrow boiling point range, but there is a problem in that they have almost no PP lowering ability. The additive of the present invention (1) exhibits excellent CFPP lowering ability for oils with both narrow and wide boiling point ranges, and is also good for heavy oils with narrow boiling point ranges;
Shows CFPP lowering ability; (2) CFPP reduction even in small amounts
Sufficient descending ability. ; (3) exhibits PP lowering ability; it exhibits the following revolutionary effects. Such effects can be clearly recognized by observing the precipitation of paraffin wax crystals under a microscope while slowly cooling fuel oil to which the additive of the present invention has been added. In other words, no matter what kind of fluidity improver is added to fuel oil with a narrow boiling point range, unless the amount added reaches 0.1% or more, the paraffin wax crystals that precipitate during slow cooling will have a large form and cannot be used for CFPP measurement. It cannot be something so minute that it can pass through the wire mesh. On the other hand, when the additive of the present invention is added in an amount of, for example, about 0.01%, the crystal form of the paraffin wax that precipitates by slow cooling becomes extremely fine, making it relatively easy to mesh the wire mesh described above. It is large enough to pass through. Since the additive of the present invention exhibits the above-mentioned effects, it is useful as an additive added for the purpose of improving fluidity in pipelines during transport of fuel oil and preventing clogging of filters. The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Example 1 Sorbitol (EO) with an average molecular weight of 1062 and a hydroxyl value of 317 ₂₀ [Represents a 20 mole ethylene oxide adduct of sorbitol. Similar expressions will be used below. ] 106.2g (0.1mol) and stearic acid 170g
Sorbitol was produced by adding (0.6 mol) and 1 g of para-toluenesulfonic acid as a catalyst to a flask equipped with a stirrer, thermometer, nitrogen blowing pipe and exhaust pipe, and reacting at 150 to 160°C for 6 hours while blowing nitrogen. (EO) ₂₀ stearic acid hexaester (light yellow solid product, acid value 2, hydroxyl value 1, saponification value 125) was used as the additive of the present invention. Example 2 Sorbitol (EO) ₂₀ 106.2g in Example 1
(0.1 mol) and 136 g (0.4 mol) of behenic acid were reacted for 6 hours in the same manner as in Example 1 using 1 g of p-toluenesulfonic acid as a catalyst, and then 30 g (0.21 mol) of 2-ethylhexylic acid was added and reacted for 6 hours. The 2-ethylhexylic acid diester of sorbitol (EC) ₂₀ behenic acid tetraester (pale yellow solid product, acid value 5, hydroxyl value 2, saponification value 130) prepared by this method was used as the additive of the present invention. Example 3 Sorbitol (PO) ₁₀ (EO) ₁₅ with an average molecular weight of 1403 and a hydroxyl value of 240 [15 moles of ethylene oxide added to a 10 mole adduct of sorbitol with propylene oxide] 140.3 g (0.1 mole) and myristic acid 45.6g (0.2mol), palmitic acid 51.2g (0.2mol), stearic acid 56.8g (0.2mol)
Sorbitol (PO) ₁₀ (EO) ₁₅ mixed fatty acids (myristic acid: palmitic acid: stearic acid =
1:1:1 weight ratio) hexaester (pale yellow solid product, acid value 2, hydroxyl value 2, saponification value
116) was used as the additive of the present invention. Example 4 186 g (0.1 mol) of sorbitol (PO) ₃₀ with an average molecular weight of 1860 and a hydroxyl value of 181 and 204 g of behenic acid.
Sorbitol (PO) ₃₀ behenic acid hexaester (pale yellow solid product, acid value 6, hydroxyl (value: 2, saponification value: 88) was used as the additive of the present invention. Example 5 80 g (0.1 mol) of sorbitol (EO) ₁₄ with an average molecular weight of 800 and a hydroxyl value of 421 and 87.5 g of oleic acid.
(0.31 mol) was reacted with 1 g of para-toluenesulfonic acid as a catalyst for 6 hours in the same manner as in Example 1, and then 102 g (0.3 mol) of behenic acid was added and reacted for 6 hours. Sorbitol (EO) ₁₄ Behenic acid triester of oleic acid triester (light yellow solid product, acid value 5, hydroxyl value 0, saponification value 134) was used as the additive of the present invention. Example 6 114 g of pentaerythritol (PO/EO=1/1) ₂₀ with an average molecular weight of 1140 and a hydroxyl value of 197
Pentaerythritol (PO/EO = 1/1) A tetraester of ₂₀ mixed fatty acids (stearic acid: behenic acid = 1:1 molar ratio) (pale yellow solid product, acid value 4, hydroxyl value 2, saponification value 95) is produced according to the present invention. It was used as an additive. Comparative Examples 1 to 4 PEG (polyethylene glycol) for comparison
600 dibehenate, sorbitol (EO) ₂₀ oleic acid hexaesters, sorbitol (EO) ₂₀ behenic acid diesters and ethylene-vinyl acetate copolymer [MW: 2500, vinyl acetate content: 32% (weight)]
were used as additives in Comparative Examples 1, 2, 3, and 4, respectively. Usage Example 1 The additives of Examples 1 to 6 and Comparative Examples 1 to 4 were added to five kinds of light oils having the properties shown in Table 1, and CFPP and pour point (PP) were measured. Table the results.
Shown in 2. (Properties of light oil)

【table】

[Table] As is clear from Table 2, the additive of the present invention can lower the CFPP of both narrow boiling point range light oil and wide boiling point range light oil with a much lower addition amount than the conventional technology. It was also found that PP can be lowered to some extent, and CFPP can be lowered for light oil with a narrow boiling point range, but PP
It has a significant advantage over PEG600 dibehenate, which cannot lower CFPP, and ethylene-vinyl acetate copolymer, which can lower PP but not CFPP for narrow boiling range gas oils. it is obvious. Also light oil
It shows good performance even with heavy oils such as No. 3 with a narrow boiling point range. Also, sorbitol (EO) ₂₀ oleic acid hexaester, which is not esterified with an aliphatic straight chain saturated fatty acid having 14-30 carbon atoms, and sorbitol (EO) ₂₀ behenic acid ester, which still has a hydroxyl group, are ineffective. It shows. Examples 7-12 Additives of the invention as follows (Examples 7-12)
I got it. (Example 7) Additive of Example 2: 20 parts Monoamide of n-tetradecenylsuccinic acid and di(n-octadecyl)amine: 80 parts (Example 8) Additive of Example 4: 20 parts Monoamide of n-tetradecenylsuccinic acid and di(n-octadecyl)amine: 80 parts (Example 9) Additive of Example 2: 10 parts n-octadecane (1.18) dicarboxylic acid and di(n-octadecyl) ) diamide with amine
: 90 parts (Example 10) Additive of Example 2 : 30 parts Diamide of trimellitic acid and di(n-octadecyl)amine : 70 parts (Example 11) Additive of Example 2 : 30 parts Tolylene diisocyanate and di(n-octadecyl)amine: 70 parts (Example 12) Additive of Example 2: 20 parts Condensate of chlorinated paraffin and naphthalene (MW: 3800): 80 parts Usage example 2 Example Light oil with additives 7 to 12 shown in Table 1.
1, 2, and 3 to measure PP and CFPP.
The results were as shown in Table 3. As is clear from Table 3, when (A) and (B) are used together,
(A) It can be seen that the descending ability of CFPP is almost the same as when used alone, but the PP descending ability is amplified and is advantageous.

【table】

Claims (1)

[Claims] 1 At least 4 hydroxyl groups and 85 to 1500
A complete ester of a polyoxyalkylene ether of a polyhydric alcohol having an equivalent weight of , a straight chain saturated fatty acid having 14 to 30 carbon atoms, and optionally other carboxylic acids; and optionally (B) a nitrogen-containing derivative of alkenylsuccinic acid, chlorine. It is characterized by containing a compound selected from the group consisting of a condensate of diparaffin and naphthalene, a nitrogen-containing derivative of a long-chain alkylene dicarboxylic acid, a nitrogen-containing derivative of tricarboxylic acid, and a reaction product of a diisocyanate compound and a dialkylamine. Flowability improving additive for fuel oil. 2 Complete ester is the general formula [In the formula, R is a residue of a polyhydric alcohol; A is an alkylene group having 2 to 4 carbon atoms; R' is a carboxylic acid residue, and at least one of the m R's has a carbon number of 14
~30 straight chain saturated fatty acid residues. m is an integer of 4 or more, n is R[-(OA) _o OH] the equivalent of _n is 85 ~
The number is 1500. ] The additive according to claim 1, which is a compound represented by: 3. The additive according to claim 1 or 2, wherein the weight ratio of (A) and (B) is 2:98 to 98:2. 4 (B) The nitrogen-containing derivative of alkenylsuccinic acid is an alkenylsuccinic acid having an alkenyl group having 14 to 22 carbon atoms or its anhydride and an alkyl group having 14 carbon atoms.
3. The additive according to any one of claims 1 to 3, which is a reaction product with a dialkylamine of .about.20.