JPS6249920B2 - - Google Patents

Description

[Detailed description of the invention]

Distillate fuel treatment additive systems to improve the flow of wax clovdy fvels through pipelines and filters in cold climates are
It is known as illustrated by the patents listed below. British Patents Nos. 900202 and 1263152 relate to the use of low molecular weight copolymers of ethylene with unsaturated esters, particularly vinyl acetate, and British Patent No. 1374051 both increases the onset temperature of wax crystallization and increases the particle size of the wax crystals. Concerning the use of limiting additive systems. The use of low molecular weight copolymers of ethylene and other olefins as pour point depressants in distillate fuels is described in British Patent Nos. 848777 and 993744.
No. 1,068,000 and US Pat. No. 3,679,380. U.S. Patent Nos. 3374073 and 3499941
No. 3507636, No. 3524732, No. 3608231,
No. 3,681,302 proposes various other specialized types of polymers as additives for distillate fuels. It has also been proposed that additive combinations can be used in distillate fuels to further improve flow and pour point properties. for example,
US Patent No. 3,661,541 relates to the combination of additives of the ethylene/unsaturated ester copolymer type with the low molecular weight ethylene/propylene copolymers of UK Patent No. 993,744. U.S. Pat. No. 3,658,493 describes various nitrogen salts of acids such as monocarboxylic and dicarboxylic acids and amides, phenols, and sulfonic acids in combination with ethylene homopolymer or copolymer pour point depressants for middle distillate oils. is listed. U.S. Pat. No. 3,982,909 discloses that nitrogen compounds such as ammonium salts of amides, diamides, monoamides and monoesters of dicarboxylic acids alone or in petroleum derived microcrystalline waxes and/or pour point depressants, especially ethylene It is described in combination with a backbone polymer pour point depressant to become a wax crystal modifier and low temperature flow improver for middle distillate fuel oils. US Patent Nos. 3,444,082 and 3,946,093 describe the use of various amide and amine salts of alkenylsuccinic anhydrides in combination with ethylene copolymer pour point depressants for distillate fuels. U.S. Pat. No. 3,762,888 discloses a first component polymer, such as an ethylene copolymer, and a second component comprising a linear polymethylene segment selected from the group of fatty acid esters, alkoxylated polyethers, alkanol esters, etc. of polyols. A flow improver for middle distillate fuel oils is described that includes a variety of characteristic organic compounds. Most importantly with respect to the present invention, this U.S. patent reports that the second component is a component that generally provides little or no flow-improving properties when used in the absence of the polymeric first component. be. The present invention describes a range of polyoxyalkylene esters, ethers, ether/esters and mixtures thereof as cold flow improving additives for distillate fuels (so-called middle distillate fuels) having a boiling point range of 120 to 500°C. The discovery that it is effective and can be used as the sole additive for narrow boiling distillate fuels (discussed later), which are effective in themselves and in many cases not effective with conventional flow improving additives. It is based on The use of such narrow boiling point distillates increases the initial boiling point of the middle distillate and increases the amount of distillate in the kerosene range which requires lowering the final boiling point of the distillate to meet cloud point specifications. The increase is due to demand from refineries to produce Therefore, these narrow boiling point distillate oils have relatively high initial boiling points and relatively low final boiling points. Generally speaking, prior art additives
Although useful for inhibiting the growth of wax crystals that separate in distillate fuel oils in the boiling range of ~500°C, especially 160°C to 400°C, further improvements are needed. However, improving the flow and perpendicularity of distillate oils with relatively narrow boiling point ranges is known to be difficult. The inventors now demonstrate that certain polyoxyalkylene esters or polyoxyalkylene ethers or polyoxyalkylene esters/ethers or mixtures thereof are particularly useful in processing narrow boiling distillate fuels to improve their flow properties. I discovered that. The term “narrow boiling point distillate fuel” refers to
This is meant to include distillate fuels with a boiling point range of 50°C to 340°C ± 20°C; fuels with boiling point characteristics outside this range are referred to as broad boiling distillate fuels. Therefore, the present invention provides at least two C ₁₀ -C ₃₀
A polyoxyalkylene having a chain saturated alkyl group and a polyoxyalkylene glycol having a molecular weight of 100 to 5,000, preferably 200 to 5,000, in which the alkylene group of the polyoxyalkylene glycol contains 1 to 4 carbon atoms. ester,
The use of ethers, esters/ethers and mixtures thereof as flow improving additives for middle distillate fuel oils, particularly narrow boiling distillate fuel oils. Furthermore, in its broader aspects, the present invention provides from 0.0001 to 0.5% by weight of the above-mentioned polyoxyalkylene esters, polyoxyalkylene ethers, polyoxyalkylene esters/ethers or mixtures thereof as a low temperature flow improving additive.
A distillate fuel oil having a boiling point range of 120°C to 500°C is provided containing 0.001 to 0.5% by weight alone or in combination with other flow improving additives. Preferred esters or ethers or esters/ethers useful in the present invention can be structurally represented by the following formula: R—O—(A)—O—R ₁ In the above formula, R and R ₁ are the same or different, and (i) n-alkyl (ii) (iii) and the alkyl group is linear and saturated and contains 10 to 30 carbon atoms, m is 1 to 3, and A is polyoxymethylene or polyoxyethylene or polyoxytri Methylene moieties [These are substantially linear, and although some degree of branching by lower alkyl side chains (such as in polyoxypropylene glycol) is acceptable, for the purposes of this invention the glycols are substantially linear. polyoxyalkylene segment of a glycol (the alkylene group in the segment has 1 to 4 carbon atoms), such that Suitable glycols generally have a molecular weight of about 100
~5000, preferably from about 200 to 2000 (the latter range being particularly useful for improving the flow properties of narrow boiling distillate oils) in substantially linear polyethylene glycol (PEG) and polypropylene glycol (PPG). be. Esters are the preferred additives of the present invention, and fatty acids containing about 10 to 30 carbon atoms are useful for reacting with glycols to produce the ester additives of the present invention; When it is intended to be used for oil extraction, it is preferred to use _C18 - _C24 fatty acids, especially behenic acid or a mixture of behenic acid and stearic acid. Esters can also be produced by esterification of polyethoxylated fatty acids or polyethoxylated alcohols. Suitable additives for use in narrow boiling distillates are polyoxyalkylene diesters, polyoxyalkylene diethers, polyoxyalkylene ethers/esters and mixtures thereof, diesters being preferred, but small amounts of monoethers. and monoesters can also be present and are often formed during the manufacturing process. Important to additive performance is the presence of a predominant amount of dialkyl compound. Particularly preferred are stearic acid diesters or behenic acid diesters of polyethylene glycol or polypropylene glycol or polyethylene glycol/polypropylene glycol mixtures. Therefore, one preferred embodiment of the invention is:
esters or ethers or esters/ethers of polyethylene glycol or polypropylene glycol with a molecular weight of 100 to 5000 and _C18 - _C24 fatty acids as a cold flow improving additive, about 0.0001 to 0.5% by weight, based on the weight of the fuel to be treated; Preferably in an amount in the range of 0.005 to 0.05% by weight to provide a narrow boiling distillate fuel as defined above with improved flow and permeability properties. When using polyethylene glycol derivatives, the molecular weight is between 200 and 1500.
Polyethylene glycol is preferred, and when polypropylene glycol is used, the molecular weight is
200-2000 polypropylene glycol is preferred. Most preferably the polyalkylene glycol has a molecular weight of 200-800. The polyoxyalkylene ester or polyoxyalkylene ether or polyoxyalkylene ether/ester can be used as the sole additive or together with other additives. The polyoxyalkylene esters or polyoxyalkylene ethers or polyoxyalkylene esters/ethers of the present invention are often effective as sole additives for narrow-boiling distillate oils for which conventional additives are generally known to be ineffective. be. However, with wide boiling point distillate fuels,
The ester or ether or ester/ether additives of the invention are preferably used in combination with other flow improving additives. Flow improving additive formulations of the above polyoxyalkylene esters or polyoxyalkylene ethers or polyoxyalkylene esters/ethers or mixtures thereof and other additives constitute another embodiment of the invention. In the broad boiling distillate fuel, the other additive is preferably a halogenated polymer of ethylene, especially chlorinated polyethylene, and more preferably a copolymer of ethylene and other unsaturated monomers. More generally, these other conventional additives will range from 3 to 40 moles per mole of second ethylenically unsaturated monomer;
Preferably it is an ethylene copolymer typically characterized as a wax crystal modifier having a vapor pressure osmosis (VPO) Mn of 500 to 10,000, containing 4 to 20 moles of ethylene. Particularly preferred are ethylene/vinyl acetate copolymer flow improvers. 90-10% by weight, preferably 50-10% by weight of the polyoxyalkylene ester or polyoxyalkylene ether of the invention,
More preferably about 20-40% by weight and 10-90% by weight of ethylene/unsaturated ester copolymer, preferably
Preferred are formulations comprising 50-90% by weight, more preferably about 80-60%. Ethylene/vinyl acetate copolymers, particularly containing 10 to 40% by weight, more preferably about 25 to 35% by weight vinyl acetate and about 1000% by weight
Ethylene/vinyl acetate copolymers having a vapor pressure osmosis (VPO) number average molecular weight of ~6000, preferably 1500-4500 are preferred co-additives. Preferred glycol esters for use in such formulations are dibehenic acid esters of polyethylene glycol having a molecular weight of 200-1500, especially 800-1500. Unsaturated monomers that can be copolymerized with ethylene have the general formula [In the above general formula, R ₃ is hydrogen or methyl, R ₂ is -OOCR ₅ group (here, R ₅ is hydrogen or
_C1 to _C28 , more usually _C1 to _C17 , preferably _C1
~C ₈ straight or branched alkyl group), or R ₂ is a —COOR ₅ group (where R ₅ is as above but not hydrogen) and R ₄
is hydrogen or -COOR ₅ as defined above]. R ₃ and R ₄ are hydrogen and R ₂ is -OOCR ₅
monomers include _C1 - _C29 , more usually _C1 - _C18 monocarboxylic acids, preferably _C2 - _C5
Contains vinyl alcohol esters of monocarboxylic acids. Examples of such esters include vinyl acetate,
Vinyl isobutyrate, vinyl laurate, vinyl myristate, vinyl palmitate are included, with vinyl acetate being the preferred vinyl ester. R ₂ is-
When COOR ₅ and R ₄ is hydrogen, such esters include methyl acrylate, isobutyl acrylate, methyl methacrylate, lauryl acrylate, C ₁₃ oxo alcohol ester of methacrylic acid, and the like. Examples of monomers when R ₃ is hydrogen and R ₂ and R ₄ are -COOR ₅ groups include fumaric acid mono C ₁₃ oxo alcohol ester, fumaric acid di C ₁₃ oxo alcohol ester,
Includes diisopropyl maleate, dilauryl fumarate, and methylethyl fumarate. The polyoxyalkylene esters or polyoxyalkylene ethers or polyoxyalkylene esters/ethers of the present invention can be blended with ionic or nonionic polar compounds capable of acting as wax crystal growth inhibitors in fuels. Can be used during fuel extraction. Polar nitrogen-containing compounds have been found to be particularly effective when used in combination with the glycol esters or ethers or glycol esters/ethers of the present invention. These polar nitrogen-containing compounds are generally prepared by reaction of at least one molar ratio of a hydrocarbyl-substituted amine with one molar ratio of a hydrocarbyl acid or anhydride having from 1 to 4 carboxylic acid groups. C ₃₀ -C ₃₀₀ , preferably C ₅₀ -C ₁₅₀ amine salts and/or amides, esters/amides can also be used. These nitrogen compounds are described in US Pat. No. 4,211,534. Suitable amines are usually long-chain C ₁₂ -C ₄₀ primary or secondary or tertiary or quaternary amines or mixtures thereof, but also short-chain amines, provided that the resulting nitrogen compound is oil-soluble. Therefore, any compound containing generally about 30 to 300 total carbon atoms can be used. The nitrogen compound must also have at least one straight chain _C8 - _C40 alkyl segment. Suitable amines include primary or secondary amines or tertiary or quaternary amines, although the preferred amines are secondary amines. Tertiary and quaternary amines can only form amine salts. Examples of amines include tetradecyl amine, cocoa amine, hydrogenated tallow amine, and the like. Examples of secondary amines include dioctadecylamine, methylbehenylamine, and the like. Amine mixtures are also suitable, and many amines derived from natural products are mixtures. Preferred amines are
Formula HNR ₁ R ₂ (wherein R ₁ and R ₂ are approximately C ₁₄ 4
%, an alkyl group derived from hydrogenated beef tallow consisting of 31% C ₁₆ and 59% C ₁₈ ). Examples of suitable carboxylic acids (and their anhydrides) for preparing these nitrogen compounds include cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, cyclopentanedicarboxylic acid, diα-
Contains naphthyl acetic acid, naphthalene dicarboxylic acid, etc. Generally, these acids have about 5 to 13 carbon atoms in the cyclic moiety. Preferred acids useful in the present invention are benzenedicarboxylic acids such as phthalic acid, terephthalic acid, orthophthalic acid. Orthophthalic acid and its anhydride are particularly preferred embodiments. The nitrogen-containing compound has 8 to
It is preferred to have at least one straight chain alkyl segment containing 40, preferably 14 to 24 carbon atoms. At least one ammonium or amine salt or amide bond must also be present in the molecule. A particularly preferred amine compound is an amide-amine salt prepared by the reaction of 1 mole part of phthalic anhydride with 2 moles of dihydrogenated beef tallow amine. Another preferred embodiment is a diamide obtained by dehydrating this amide-amine salt. Formulations that have been found to be particularly useful for wide boiling distillate fuels include about 10 to 90%, preferably 50 to 80%, more preferably 60 to 80% by weight of the above nitrogen compounds and the additives of the present invention. About 90-10% by weight, preferably 50-20% by weight, more preferably 20% by weight of polyoxyalkylene esters or polyoxyalkylene ethers or polyoxyalkylene ethers/esters or mixtures thereof used as
~40% by weight; such formulations and fuels containing such formulations are also embodiments of the present invention. According to another embodiment of the invention, the fuel oil composition may also include a lubricating pour point depressant. This has been found to be useful in improving the flow properties of distillate fuels with high final boiling points, particularly those with final boiling points above 385°C. Examples of preferred lubricating oil pour point depressants are linear waxes with alkyl aromatic hydrocarbons, preferably aromatic hydrocarbons such as naphthalene, such as those produced by Friedel-Crafts condensation of halogenated waxes. . Typically suitable halogenated waxes are those containing 15 to 60, for example 16 to 50, carbon atoms and 5 to 25% by weight, preferably 10 to 18% by weight of halogen, preferably chlorine. It is. Alternatively, the lubricating oil pour point depressant may be a known oil soluble ester and/or higher olefin polymer; if so, the lubricating oil pour point depressant may be a lube oil pour point depressant, such as a Meklorab Vapor Pressure Osmometer ( Mechrolab Vapor Pressur
The number average molecular weight, as determined by vapor pressure osmosis, such as by Osmometer, or by gel permeation chromatography, generally ranges from about 1000 to 200,000, such as from 1000 to 100,000, preferably from 1000 to 50,000. These second polymers include copolymers with other unsaturated monomers such as olefins other than ethylene. Typical polymers are described in published UK Patent Application No. 2023645A. The relative proportions of polyoxyalkylene ester or polyoxyalkylene ether or polyoxyalkylene ester/ether and lubricating oil pour point depressant and other additives to be used depend, among other things, on the nature of the fuel. However, it is preferred to use 0 to 50% by weight, preferably 5 to 30% by weight of lubricating oil pour point depressants, based on the total amount of additives present in the distillate fuel. The fuel may also contain 0-90% by weight of other additives of the type described herein. The additive system of the present invention can be conveniently supplied as a concentrate in oil of an ester or ether of a polyoxyalkylene glycol or an ester/ether or a mixture thereof for addition into a bulk distillate fuel. These concentrates preferably contain from 3 to 75%, more preferably from 3 to 60%, most preferably from 10 to 50% by weight of additives.
Preferably, it is included in the form of a solution in oil. Such concentrates are also within the scope of this invention. In short, the present invention provides at least two C ₁₀ ~
Ester or ether or ester containing a C ₃₀ chain saturated alkyl group and a polyoxyalkylene glycol having a molecular weight of 100 to 5000, for example 200 to 5000, in which the alkylene group in the polyoxyalkylene has 1 to 4 carbon atoms. Polyoxyalkylene substances that are ethers or mixtures thereof10~
flow improver 0.0001-0.5% by weight, including 100% by weight
For example, 0.001 to 0.5% by weight and copolymers of ethylene and other unsaturated monomers such as vinyl acetate.
90% by weight, for example from 50 to 90% by weight, and C ₃₀ which is an amine salt and/or amide and/or ester/amide of a carboxylic acid or anhydride thereof having 1 to 4 carboxylic acid groups.
-C ₃₀₀ oil-soluble polar nitrogen compound 0-90% by weight, e.g. 50-90% by weight, and 0-50% by weight, e.g. 5-90% by weight a lubricating oil pour point depressant.
Boiling range with improved low temperature flow properties by 30% by weight
Includes distillate fuel oils with a boiling point range of about 120°C to 500°C, including narrow boiling distillate oils of 200±50°C to 340°C±20°C. The flow improver may be a polyoxyalkylene material alone or a blend of a polyoxyalkylene material and one or more of the other components listed above. Other additives may also be present. The present invention will be further explained below with reference to Examples, but these Examples should not be considered as limiting the scope of the present invention. In the Examples, the fuel used in the tests had the properties shown in Table 1.

[Table] These fuels are typical of European heating and diesel fuels. Fuel A, B, C, D
is a narrow boiling point distillate fuel (Narrow Boiling
Distillates) (NBD), E, F, H,
I is broad boiling distillate fuel
(BBD), where G is on the boundary between narrow boiling point and wide boiling point. In one method, the response of oil to additives is
“Journal of the Institute
Journal of the Institute
of Petroleum)”, Volume 52, No. 510, June 1966,
Cold Fllter Plugging Point Test performed as detailed on pages 173-185.
(CFPPT). This test is designed to correlate with cold flow of middle distillate fuel in an automatic diesel engine. Briefly, a 40 ml sample of the oil to be tested is cooled in a bath maintained at about -34°C to provide non-linear cooling at about 1°C/min. Periodically (starting at a temperature of at least 2° C. above the cloud point and each time the temperature decreases by 1° C.), the cooled oil is pipetted at the bottom end with an overturning funnel below the surface of the oil being tested. Test equipment is used to test the ability to flow through a fine screen at a given time. The funnel mouth has a diameter of 12mm.
A 350-mesh screen with a limited area is installed. Each cyclic test applies a vacuum to the top of the pipette, thereby drawing oil through the screen and into the pipette up to the 20 ml mark. If the passage is successful, return the oil to the CFPP pipe immediately after passage. This test is repeated for each 1° decrease in temperature until the oil no longer fills the pipette within 60 seconds, and this temperature is
Temperature. The difference between the CFPP of a fuel without an additive and the CFPP of the same fuel with an additive is the CFPP drop due to the additive. A more effective flow modifying additive will give a greater CFPP drop for the same additive concentration. Flow improver distillate operability test, which is a slow cooling test designed to correlate with pumping of stored heating oil
Another measurement of flow improver effectiveness is made under conditions of (DOT test). Determination of the cold flow properties of the fuel containing additives by DOT test is carried out as follows. 300 ml of fuel is cooled linearly at a rate of 1° C./hour to the test temperature and then held constant at that temperature. After keeping at the test temperature for 2 hours, the surface layer about 20
ml is removed by suction to ensure that the test is not influenced by unusually large wax crystals that tend to form at the oil/air interface during cooling. After dispersing the settled wax in the bottle by gentle stirring, insert the CFPPT filter device. Open the stopper and apply a vacuum of 500mmHg, and when 200ml of fuel passes through the filter and enters the scaled receiver, close the stopper and pass through the specified mesh size.
If the flow rate is within seconds, it is considered a pass; if the flow rate is too slow, indicating that the filter is clogged, it is a fail. Messenger number 20, 30, 40, 60, 80, 100, 120,
Using CFPPT filter devices with 150, 200, 250, 350 filter screens, the finest mesh through which the fuel passes (maximum mesh number)
Measure. The higher the mesh number that the wax-containing fuel passes through, the smaller the wax crystals and therefore the greater the effectiveness of the water flow improvement additive. It should be pointed out that no two fuels will give exactly the same test results for the same flow improvement additive at the same treatment concentration, so the actual treatment concentration will vary somewhat from fuel to fuel. Distillate oil flow improver A1 used in the examples
GB 1,374,051 and its corresponding US Pat. It is a concentrate of about 50% by weight of a mixture of ethylene-vinyl acetate copolymer in an aromatic diluent. More specifically, the two polymers are in a ratio of about 75% by weight wax growth inhibitor to about 25% by weight nucleating agent. The wax growth inhibitor consists of ethylene and about 38% by weight vinyl acetate and has a number average molecular weight of about 1800 (VPO).
This is described as Copolymer B of GB 1374051, Example 1 (column 8, lines 25-35) and correspondingly described in US Pat. No. 3,961,916, column 8, lines 32. The nucleating agent is ethylene and about 16
% by weight of vinyl acetate, and has a number average molecular weight of approximately 3000 (VPO). Copolymer H (columns 7-8,
(see Table 1) and is described in corresponding U.S. Pat. No. 3,961,916, column 8, line 45. Distillate flow improver A2 is the wax growth inhibitor component of A1 used alone. Polyethylene glycol (PEG) esters and polypropylene glycol (PPG) esters are prepared by mixing 1 molar ratio of glycol with 1 molar ratio or 2 molar ratios of carboxylic acid for "mono" and "di" esters, respectively. Manufactured by. 0.5% by weight of the reaction mass of p-toluenesulfonic acid was added as a catalyst. The mixture was heated to 150° C. with stirring, and the water of reaction was distilled off with a slow flow of nitrogen. When the reaction was complete as judged by infrared spectroscopy, the product was poured out while melting and allowed to cool to give a waxy solid. The product was identified by elemental analysis, gel permeation chromatography, saponification, and spectroscopic methods. PEG and PPG are usually referred to in combination with their molecular weight, for example PEG600 has an average molecular weight of 600
polyethylene glycol. This nomenclature is also used herein for esters, PEG600
Dibehenate is composed of 2 molar ratios of behenic acid and 1 molar
It is an ester product with PEG600. Mixtures of PEGs of different molecular weights can also be used.
For example, mixed PEG (200/400/600) distearate is 1:1 of PEG200, PEG400, and PEG600.
A 1:1 weight ratio mixture of distearate esters. Mixtures of carboxylic acids can also be used. For example, PEG di(stearate/behenate) is the product of one mole of PEG and one mole each of stearic acid and behenic acid. In mixtures of both types, two, three or several
PEG or PPG or PEG/PPG copolymers and carboxylic acids can be used. Examples of polar monomer nitrogen-containing growth inhibitors include:
The following compounds (hereinafter referred to as "B1", "B2", "B3", and "B4") were used. B1: A reaction product obtained by reacting 1 mole of phthalic acid with dihydrogenated beef tallow amine to produce a half amine/half amide salt. B2: Phthalic acid diamide obtained by removing 1 mole of water from 1 mole of B1. B3: Dihydrogenated tallow amine salt of monooctadecyl phthalate. B4: Diamide product obtained by reaction of 2 moles of dihydrogenated tallow amine with 1 mole of maleic anhydride and dehydration. Although many additives can be used as oil solutions, the active ingredient used in the examples is the actual amount of additive. Example 1 CFPP, a narrow-boiling distillate fuel that is normally difficult to process, containing the polyoxyalkylene ester of the present invention
The performance in the test was compared to that of the same fuel containing an ethylene vinyl acetate (EVA) copolymer additive.
Comparing the performance with the CFPP test, the following results were obtained.

[Table] Tween 65 is polyethoxylated sorbitan tristearate (non-linear). These results indicate that in these fuels, only
100 ppm of PEG ester causes significant CFPP reduction, but 500 ppm of EVA shows no effect. Example 2 The performance of the fuel used in Example 1 containing the polyglycol ester of the present invention in the DOT test at a temperature 5°C to 7°C lower than the fuel WAP (shown in Table 1) was evaluated. Comparisons were made with the commercially available flow improver, and the following results were obtained.

TABLE These results demonstrate the advantage of PEG esters as flow improvers in these fuels when compared to various conventional flow improvers.
It is also shown that PEG esters are advantageous over the non-linear ethoxylated ester "Twwen65". In the table, B20 indicates that the sample did not pass through 20 mesh screens (the same applies below). Example 3 The performance of Fuel A of Table 1 containing 100 ppm of various polyoxyethylene dibehenate additives with polyoxyethylene segments of different number average molecular weights was determined at -15°C using the DOT test. The results were as follows.

【table】

Table: This shows that esters of PEG with a molecular weight of 200 to 600 are advantageous and preferred. Example 4 Example 3 was repeated using 100 ppm of a diester of polyethylene glycol with a molecular weight of 600 esterified with 2 moles of carboxylic acids of different chain lengths as the polyglycol ester. The results were as follows.

[Table] Stearate/Behenate
The mixed stearate/behenate is obtained by reacting 2 moles of an equimolar mixture of stearic acid and behenic acid with polyethylene glycol. This example shows that PEG esters of high molecular weight carboxylic acids are advantageous, and also shows that esters of PEG, alone or mixed, and mixtures of carboxylic acids are advantageous. Example 5 The water flow improving effectiveness of PEG esters in Fuel A of Table 1 was determined using the DOT test (at -15°C).
A comparison was made with PPG ester and also with a mixture of PPG ester and PEG ester.

【table】

Table: These results indicate that PPG di(stearate/behenate) is also a very effective flow improver at high concentrations, but is not as effective as PEG esters at lower concentrations. The effectiveness of PPG ester is
It is also shown that it depends on the PPG molecular weight. Mixtures of PPG and PEG esters can also be used effectively. Example 6 The CFPP drop of Fuel D in Table 1 containing PEG esters obtained by esterification of PEG of various molecular weights with various carboxylic acids was measured and the following results were obtained.

【table】

[Table] Dibehenate These results show that PEG400 dibehenate and
PEG600 dibehenate is shown to have both the optimum PEG molecular weight and optimum carboxylic acid for CFPP reduction of this fuel. For comparison,
The CFPP drop for Fuel D containing 100 ppm Additive A1 was -1. Example 7 The effectiveness of a blend of PEG ester and other additives in NBD was determined in a DOT test in Fuel B of Table 1 at -15°C.

TABLE These results demonstrate that the blend of PEG ester and polar monomer B1 is advantageous over either alone and over the B1/Tween 65 blend. The performance of EVA copolymer A2 is also improved by the presence of PEG ester. Example 8 The effectiveness of a PEG ester blended with an ethylene/vinyl acetate copolymer growth inhibitor as a CFPP depressant for Broad Boiling Fuel E of Table 1 was as follows.

Table: These results show that such formulations are significantly more effective than the ingredients alone. Example 9 The effectiveness of PEG esters blended with polar monomer compounds as CFPP depressants in Fuel F of Table 1 is as follows.

[Table] Henate
These results indicate that when used in combination with A2,
PEG dibehenate is shown to be advantageous over distearate and to use components such as PEG600 dibehenate in this application. We also show that polar monomeric compounds can be effective CFPP lowering agents when used in combination with PEG600 esters. Example 10 In this example, the DOT test at -12°C
Testing the effectiveness of the PEG ester/A2 formulation.

TABLE These results demonstrate that the effectiveness of blends of EVA copolymer wax crystal growth inhibitors or polar monomer wax crystal growth inhibitors with PEG esters is greater than equal concentrations of growth inhibitor alone. Example 11 In this example, 25 ^m3 tank 3 of fuel D in Table 1 was used.
Test the pieces side by side. After 3 weeks of storage under natural cold conditions (including natural temperature cycling), at -13.5°C,
As at the fuel distribution station, the fuel was pumped from the tank and the finest filter screen through which the fuel flowed was noted.

[Table] The filter screen normally used in such fuel distribution devices is a screen with mesh number 60, therefore the fuel containing EVA copolymer A1 is
It is found that fuels containing PEG ester alone and fuels containing EVA copolymer/PEG ester blends provide satisfactory flow when pumping, although they clog the mesh filter and therefore do not provide satisfactory performance. Example 12 Rotaru containing fuel A in Table 1 was heated to 0.5℃/
After cooling to −13° C. at a rate of 100 mL and a cold soak period, the low temperature performance of 300 ml fuel samples was tested as in the DOT test. The barrel is then gradually heated to a temperature above the WAP of the fuel and then cooled again to -13°C at a rate of 0.5°C/hour. This fuel was then pumped through a range of filter screens and the finest filter screen that the waxy fuel could pass through was measured.

[Table] Dibehenate From these results, PEG ester and PEG
The advantage of the ester/PPG ester blend over the ethylene/vinyl acetate copolymer A1 is reaffirmed. Example 13 A comparison is made between linear saturated esters and linear unsaturated esters such as oleic esters using the DOT test at a test temperature of -10°C.

[Table]
D None 0 B20
Example 14 DOT tests are repeated on a series of three broad-boiling distillate fuels to show that linear PEG esters are effective even when used alone in such fuels. To demonstrate the criticality for linear saturated alkyl esters, ethylene-vinyl acetate copolymer A2
Also shown are comparative data for dioleate esters.

[Table] 〓 〓 〓 〓 〓 〓 〓 〓 〓 〓 〓 〓 〓
〓 〓 〓 〓 〓 〓 〓 〓 〓
Example 15 The following characteristics Cloud point (°C) +4 Wax appearance point (°C) -0.7 CFPP (°C) - Untreated -5 Relatively high boiling point fuel with ASTM D86 distillation initial boiling point, °C 185 End point, °C 386 were treated with various amounts of an additive mixture consisting of a blend of 1 part by weight of PEG(600) dibehenate and 4 parts by weight of Additive A2 with the following results. Additive treatment rate, ppm CFPP, °C 150 −14 200 −14 250 −14 300 −14 350 −16 450 −16 500 −16 550 −7 650 −7 In this example, the CFPP value is This is the actual temperature at which the test will fail. Chlorinated to approximately 14.5% chlorine by weight based on the weight of the chlorinated wax, melting point approximately 51.6-53.9°C
Wax naphthalene (known as C) produced by Friedel-Crafts condensation of about 100 parts by weight of n-parfine wax (125-129〓) with about 12 parts by weight of naphthalene, based on the total weight of the additive. When 10% by weight was added to the fuel containing the mixture used above,
The CFPP performance was as follows.

For example, these data show that further improvements are obtained in this fuel with the addition of C. Example 16 A comparison was made between PEG 600 distearate and PEG 600 diisostearate at a treatment rate of 200 ppm additive using the DOT test on Fuel A at a temperature of -15°C. The results were as follows.

[Table] Thus, it can be seen that linear alkyl groups are advantageous. Example 17 Polytetramethylene glycol “Teracols” with molecular weights 650, 1000, and 2000 and general formula HO—[(CH ₂ ) ₄ —O] _o —H was produced and esterified with 2 moles of behenic acid. . These esters were then subjected to DOT testing in Fuel A at a temperature of -15°C with the following results.

[Table] Dibehenate
Thus, although Delacol derivatives are active,
When compared with Example 3, it can be seen that the activity is lower than the corresponding PEG ester and PPG ester. Example 18 Ethoxylation of a C ₁₈ linear alcohol and esterification of the resulting product with 1 mole of behenic acid gave the following structure: ester ether was obtained. This additive is present in Fuel A at a concentration of 200 ppm.
Passed 80 mesh in the DOT test at -15℃. Example 19 After reacting PEG600 with 2 moles of succinic acid,
The reaction product is converted into a C ₂₂ /C ₂₄ mixed linear saturated alcohol 2
The product reacted with mole I got it. This is defined as cloud point +4℃, wax appearance point 0℃,
The test was conducted in Fuel J with CFPP performance of -1°C, initial boiling point of 195°C, and final boiling point of 375°C. This product was stored at -6°C.
Tested in the DOT test, without the additive it passed a 40 mesh screen, while with 200 ppm of additive it passed an 80 mesh screen. When 200ppm of this additive is added to fuel A,
Passed 100 meshes in the DOT test at -15℃. Example 20 Cloud point -2℃, wax appearance point -6℃, initial boiling point 200
The effectiveness of PEG(600) dibehenate was compared to that of PEG(600) dierkate in Fuel K at 354°C and an end point of 354°C. The CFPP of the untreated fuel was -7°C, which did not change with the addition of PEG(600) dierkate, but with PEG(600) dibehenate, the CFPP was -7°C.
°C, demonstrating the importance of the alkyl group being saturated. Example 21 A mixture of 4 parts of distillate flow improver A2 and 1 part of various PEG dibehenates was subjected to CFPP testing in Fuel E with the following results.

[Table] Condensate of.
Example 22 Example 21 was repeated using a teracol derivative in place of PEG dibehenate with the following results.

[Table] Example 23 Cloud point -4℃, wax appearance point -6℃, untreated
Various additives were tested in the DOT test at -10°C in Fuel L with CFPP -6°C, initial boiling point 216°C, final boiling point 353°C. The results were as follows.

[Table] Nate

[Table] Example 24 The CFPP drop of Fuel D containing various additives was as follows.

【table】

Claims (1)

[Scope of Claims] 1 A polyoxyalkylene glycol having at least two C ₁₀ to C ₃₀ chain saturated alkyl groups and a molecular weight of 100 to 5,000, wherein the polyoxyalkylene glycol has 1 to 4 alkylene groups. Cold flow improving additive for distillate fuel oils having a boiling point range of 120 to 500°C containing polyoxyalkylene esters or polyoxyalkylene ethers or polyoxyalkylene esters/ethers or mixtures thereof containing carbon atoms. . 2 Polyoxyalkylene ester or ether or ester/ether or a mixture thereof has the general formula: R—O—(A)—O—R ₁ [In the above general formula, R and R ₁ are the same or different; (i) n-alkyl (ii) (iii) , the alkyl group is linear and saturated and contains 10 to 30 carbon atoms, m is 1 to 3, and A is a polyoxyalkylene glycol with a molecular weight of 100 to 5000 (the The additive according to claim 1, wherein the alkylene group of the polyoxyalkylene glycol contains 1 to 4 carbon atoms. 3. A polyoxyalkylene glycol containing at least two _C10 to _C30 chain saturated alkyl groups and a molecular weight of 100 to 5000, in which the alkylene group of the polyoxyalkylene glycol contains 1 to 4 carbon atoms. or a polyoxyalkylene ester or polyoxyalkylene ether or polyoxyalkylene ester/ether or mixtures thereof.
Distillate fuel oil having a boiling point range of 120-500°C, containing 0.0001-0.5% by weight. 4 Polyoxyalkylene ester or ether or ester/ether or a mixture thereof has the general formula: R-O-(A)-O-R ₁ [In the above general formula, R and R ₁ are the same or different; (i) n-alkyl (ii) (iii) , the alkyl group is linear and saturated and contains 10 to 30 carbon atoms, m is 1 to 3, and A is a polyoxyalkylene glycol with a molecular weight of 100 to 5000 (the The distillate fuel oil according to claim 3, wherein the alkylene group of the polyoxyalkylene glycol contains 1 to 4 carbon atoms. 5. A polyoxyalkylene glycol containing at least two _C10 to _C30 chain saturated alkyl groups and a molecular weight of 100 to 5000, in which the alkylene group of the polyoxyalkylene glycol contains 1 to 4 carbon atoms. Cold flow improving additives containing polyoxyalkylene esters or polyoxyalkylene ethers or polyoxyalkylene esters/ethers or mixtures thereof with
0.0001 to 0.5% by weight and C which is an ethylene copolymer wax crystal growth inhibitor or an amine salt and/or amide and/or ester/amide of a carboxylic acid or its anhydride having 1 to 4 carboxylic acid groups ₃₀ - C Distillate fuel oil that also contains ₃₀₀ oil-soluble polar nitrogen compound wax crystal growth inhibitors.