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Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to blends of alkyl aromatic hydrocarbons and ethylene-containing polymers or succinamide derivatives to improve the cold flow properties of distillate fuel oils.

Kerosene, the wax solvent, has traditionally been a component of distillate fuel oils (eg, diesel fuel, home heating oil, etc.).

Since kerosene must be used in jet fuel, the amount of kerosene used in distillate fuel oils has decreased over the years.

As a result, wax crystal modifiers (eg, pour point depressing additives) often have to be added to fuel oils to compensate for kerosene deficiencies.

One group of pour point depressing additives are alkylated aromatic hydrocarbons, particularly wax-naphthalene pour point depressants.

These additives are used in various petroleum oils such as lubricating oils (e.g. US Pat. Nos. 1,815,022 and 2).
297292), other synergistic additives (co-ad
as a dewaxing aid (e.g., U.S. Pat. Nos. 341.701.0 and 34
No. 75,321) and as a pour point depressant for middle distillate fuels (see U.S. Pat. No. 32'45,366).

Another group of pour point depressing additives are ethylene-containing polymers.

Among these polymers, those that are highly effective for distillate fuel oils are copolymers of ethylene and other monomers, such as copolymers of ethylene and vinyl esters of lower fatty acids such as vinyl acetate. copolymer (US Pat. No. 3,048,479),
Copolymer of ethylene and alkyl acrylate (Canada).

Examples include terpolymers of ethylene and vinyl esters and alkyl fumarates (US Pat. Nos. 3,304,261 and 3,341,309), and polymers of ethylene and other lower olefins.

Also, ethylene. Polymer (British Patent No. 84877)
No. 7 and No. 993,744) and chlorinated polyethylene (Belgium Patent No. 707,371) are also currently known as distillate fuel oil pour point depressants.

Yet another group of pour point depressants are N-aliphatic hydrocarbyl succinic amides and their amine salts with two substituents on the nitrogen atom, U.S. Pat.
No. 2 and No. 3544467.

According to the present invention, a blend of an alkylated aromatic hydrocarbon and (B) an ethylene-containing polymer pour point depressant or (q) the above-mentioned N-aliphatic hydrocarbyl-cono-phosphate amide and its amine salt is used as a distillate fuel. It is based on the discovery that it is particularly useful as an oil flow improver.

Although many of the prior art additives described above are very effective in lowering the pour point of distillate fuel oils, they do not sufficiently reduce the particle size of the wax crystals that sometimes form.

These large wax particles tend to be collected by screens and other filtration devices commonly used on trucks and in fuel oil storage facilities, so that even when the temperature of the fuel oil is well above its pour point, These sieves and filtration devices become clogged.

The formulations of the present invention can control wax crystal particle size much more effectively than the component additives alone.

Because of this increased effectiveness of wax grain size control, the additive formulations of the present invention are suitable for use in diesel fuels in view of the current trend and desire to raise cloud points by increasing distillation temperatures. Particularly useful.

One of the advantages of increasing the cloud point is that the fuel obtained in this case contains a high proportion of high molecular weight hydrocarbons, which increases the BTU value of the fuel, and the higher the BUT value, the better the diesel engine. Economical during operation (eg diesel trucks).

The wax crystal grain size of these fuels often needs to be adjusted.

For example, in normal operation of a Diesel, YV truck, a diesel engine typically has about 50
It is equipped with a fine-mesh filter (for example, roughly comparable to a 270-mesh sieve).

In cold climates where the ambient temperature is below the cloud point, it becomes especially essential that the crystals that form are sufficiently fine to pass through the filter.

As previously stated, the present invention provides additive formulations that reduce or control the particle size of wax crystals to improve cold flow properties.

Generally, the compositions of the present invention contain a small amount of a flow-improving amount of an alkyl aromatic hydrocarbon and (B) an ethylene polymeric pour point depressant or (C) an N-aliphatic hydrocarbyl succinic acid amide or amine thereof. 0.3 to 10 parts by weight of A per 1 part by weight of normal (B) or (C) with salt;
Preferably Q, consisting mostly of 5 parts distillate fuel oil, the flow properties of which have been improved by the addition of blends in a relative proportion of 5 to 5 parts by weight.

Generally, the distillate fuel oil of the present invention has a boiling point range of 121.1°C to
482.2°C, and the cloud point is typically about -28.9°C to about 7.2°C.

The fuel oil may be a straight run or cracked gas oil, or a mixture of straight run, pyrolysis distillate and/or catalytic cracking distillate in any proportion.

It is the most common petroleum middle distillate fuel and heating oil.

Cold flow problems are most common with diesel fuels and heating oils.

Typical heating oil specifications have a 10% distillation point of approximately 226.7.
℃ or less, 50% distillation point is about 271.1℃ or less, 90% distillation point is 282.2℃ or more, about 337.8 to 343.3℃
We require the following:

However, some of the standard values have a 90% distillation point as high as 357.2°C.

Typical specifications for diesel fuel are a flash point of 37.8°C or higher and a 90% distillation point (ASTM-1160) of 282.2.
C to 337.8 C (see ASTM D-496 and D-975).

One example of high cloud point diesel fuel has an initial boiling point of approximately 176.7.
℃, 90% distillation point is about 398.4℃, final boiling point is about 452℃
．． 4.4°C cloud point fuel at 8°C (ASTM-D-1
160).

Alkyl aromatic hydrocarbons are usually produced by Friedel-Krach condensation of halogenated paraffins or olefins with aromatic hydrocarbons.

These materials are known in the art primarily as lubricating oil pour point depressants and dewaxing aids, as discussed above.

Typically,... rogenated paraffins have about 15 to about 60 carbon atoms (e.g., 16 to about 50 carbon atoms) and about 5
~25% by weight (e.g. 10-18% by weight) of cloud elements.

Typically, halogenated paraffins have a melting point of about 37.8
It is produced by chlorinating paraffin wax in the range of ~93.3°C to the above chlorine content.

The aromatic hydrocarbons used contain up to three substituents and/or fused rings.

The aromatic hydrocarbon may be a hydroxy compound such as phenol, cresol, xylenol, or an amine such as aniline, but is preferably naphthalene, phenanthrene or anthracene.

Generally, ethylene-containing polymeric pour point depressants have a polymethylene backbone segmented by hydrocarbon or oxy-hydrocarbon side chains.

These oil-soluble polymers generally have a number average molecular weight of about 500 to 500, as measured with a vapor pressure osmometer such as the Fukurolab Paper Pressure Osmometer Model 310A.
00, preferably from about 1.000 to about 5000.

Generally, ethylene-containing polymeric pour point depressants contain a ratio of about 3 to 40 (preferably 4 to 20) moles of ethylene to each mole of the second ethylenically unsaturated monomer; The monomer may be a single monomer or a mixture of such monomers in any ratio.

The unsaturated monomer copolymerizable with ethylene has the general formula (in the above general formula, R1 is hydrogen or methyl, R2
is 100CR4 or -COOR4 group, where R
4 is hydrogen or C1-C06, preferably C1-C4
straight or branched alkyl groups, R3 is hydrogen or -COOR, and unsaturated mono- and diesters thereof.

For monomers in which R1 and R3 are hydrogen and R2 is 10OCR4, monocarboxylic acids of 02 to C1□ (preferably C
(2-C5 monocarboxylic acids) vinyl alcohol esters.

Examples of such esters include vinyl acetate, vinyl isobutyrate, vinyl laurate, vinyl myristate, vinyl palmitate, and the like.

Esters in which R2 is -COOR4 include methyl acrylate, isobutyl acrylate, methyl methacrylate, lauryl acrylate, C□3 oxo alcohol ester of methacrylic acid, and the like.

Examples of monomers in which R1 is hydrogen and R2 and R3 are -COOR, include mono- and diesters of unsaturated dicarboxylic acids, such as fumaric acid mono C13 oxo alcohol ester, fumaric acid di-C13 oxo alcohol ester,
These include diisopropyl maleate, dilauryl fumarate, and ethylmethyl fumarate.

Another group of monomers that can be copolymerized with ethylene are C3~
It is a C16 alpha monoolefin, which may be linear or branched, and includes, for example, propylene, isobutyne, n-octene-1, inoctene-1, n-decene-1, dodecene-1, and the like.

Another monomer is vinyl chloride, which gives essentially the same results as ethylene chlorinated to a chlorine content of about 5-35% by weight.

Branched polyethylene itself can also be used as a pour point depressant.

These polyethylene and ethylene copolymer pour point depressants are generally made using free radical promoters, or in some cases by thermal polymerization, or in the case of ethylene and other olefins, by Ziegler-type polymerization. can do.

Although polymers made by free radical polymerization are considered more important, they can be made by: solvents and monomers other than ethylene (e.g. ester monomers) used in the batch. 0-50% by weight of the total amount of
into a stainless steel pressure vessel equipped with an agitator and a cooling coil.

Next, adjust the temperature of the pressure vessel to the desired reaction temperature (e.g. 70℃~
250°C) and ethylene to the desired pressure (e.g. 56°24-703 kg/cd gauge pressure, usually 63.27-703 kg/cd).
Pressurize to 421.8 kg/crA gauge pressure).

A promoter (usually diluted with the reaction solvent) and an additional amount of a second monomer (eg, an unsaturated ester) are added to the vessel continuously, or at least intermittently, during the reaction period.

This continuous addition provides a more uniform copolymer product than if all the unsaturated ester were added at the beginning of the reaction.

Also, during this reaction period, as the ethylene is consumed by the polymerization reaction, additional ethylene is added to the reaction line through a pressure regulator to ensure that the desired reaction pressure is maintained correctly and constant throughout the reaction period. After completion (usually a total reaction time of 1/4 to 10 hours is sufficient), the liquid product is removed from the pressure vessel and the solvent is removed by stripping, leaving the polymer as a residue.

U.S. Patent No. 3444 for succinamic acid derivatives
No. 082 and No. 3,544,467 as follows: Alkenylsuccinamides, preferably n-aliphatic hydrocarbyl succinamides, have the general formula:

In the above formula, R is bonded to the succinyl group through a secondary carbon atom,
A straight chain aliphatic hydrocarbon group (alkyl or alkenyl) having 0 to 1 olefinic unsaturation, at least 14, typically 15 to 40 carbon atoms, more usually 15 to 30 carbon atoms has carbon atoms.

One of X and Xl is hydroxyl and the other is -NYY' It is.

Here, N has the usual meaning of nitrogen, and Y and Yl are aliphatic hydrocarbyl groups, each having 14 to 14 carbon atoms.
40, more usually 15-30, and the total number of carbon atoms is about 14-28, more usually 32-48, preferably 32-40.

Y and Yl are aliphatic saturated or unsaturated hydrocarbon groups, but generally do not contain acetylenic unsaturation (
alkyl or alkenyl).

It can have 1-2 olefinic unsaturations.

Y and Yl may be the same or different, and may be linear or branched, but preferably linear.

The branched chain usually has no more than one carbon atom, ie methyl.

The bonding position of the nitrogen atom may be a terminal carbon atom or an intermediate carbon atom.

As is clear from the above formula, it is not important in which position the alkyl or alknyl group is with respect to the carboxamide or carboxyl group.

Due to the bulky nature of amines, the usual preparation from succinic anhydride results in the main product having an alkenyl group in the beta position relative to the carboxamide.

This derivative is preferable in that it can be easily produced.

However, as far as practicability is concerned, either isomer
Alternatively, a mixture of two isomers can also be used.

Technical compounds or mixtures of compounds can be used.

Mixtures of various C- and/or N-substitutions, both homologues and isomers, are often used when individual precursors to the succinamide product are not available.

Examples of succinic acid include N-N-dihexadecylhexadecylsuccinimide, N-hexadecyl, N-
Octadecyl octadecyl succinimide, N-N-dihexadecenyl C□5-2o alkenyl succinimide, N-hexadecenyl, N-eicosenyl octadecyl succinamide, N-N--:) octadecenyl ct
a-18 flukenyl succinic acid amide, etc. are included.

As previously mentioned, succinic acid amide can be used as its amine salt, and is preferably used as a mixture of acid and amine salts.

The amine salt or acid or mixture thereof can be represented by the following formula.

In the above formula, R is as defined above, and X2 and X3
is -NYY', where Y and Yl are as defined above.

The other of X2 and (There is at least one ether oxygen in the beta position to the nitrogen atom in the group bonded to the nitrogen atom).

Y2 and Y3 can also be combined to form a 5- to 7-membered heterocyclic ring containing only nitrogen and oxygen as heteroatoms.

In this case, n is 0 to 1, preferably 0.1 to 0.9
It is.

i.e. 10 to 90 mos of succiamide present.

% is in its salt form.

The aliphatic hydrocarbon group is preferably saturated and, if unsaturated, has no more than two ethylenically unsaturations.

The total number of carbon atoms in HNY2Y3 is O to 6o, usually 1
~40.

The groups mentioned above for Y and Yl can also be used for Y2 and Y3.

However, as mentioned above, primary amines can be used as well as secondary amines to form salts.

Typically, as explained below, when an amine other than the amine used to make succinamic acid is used in salt formation, a mixture of salts is obtained, combining the added amine with the secondary amine used to make succinamic acid. both participate in salt formation.

Examples of amines that can be used for salt formation are di-butylamine, heptylamine, dodecylamine, octadecylamine, tert-butylamine, morpholine, diethylamine,
These include methoxybutylamine and methoxyhexylamine.

In the present invention, the alkyl or alkenyl succinamic acid is prepared by mixing the alkyl or alkenyl succinic anhydride and the desired secondary amine in an equimolar amount between 65.6°C and 121°C.
It can be easily prepared by reaction at a temperature in the range of 1° C. without a solvent or in the presence of an inert solvent.

Reaction times generally range from 15 minutes to 1 hour.

This reaction is well known in the art and need not be discussed in detail here.

The alkyl or alkenyl succinic anhydrides used can be individual compounds or mixtures of compounds.

That is, different alkyl or alkenyl groups having different numbers of carbon atoms or attached at different positions relative to the succinic anhydride can be used.

It is also possible to use a single isomer.

Mixtures are generally readily available and are therefore preferred.

Mixtures of aliphatic hydrocarbyl-substituted succinic anhydrides are often used in which no single homologue is present in an amount of 25 mole % or less and each homolog is present in an amount of 5 mole % or more.

The secondary amines can be used either with the same aliphatic hydrocarbon group or with different aliphatic hydrocarbon groups.

Attached to the nitrogen are alkyl or alkenyl substituents, each substituent having at least 14 carbon atoms.

The extent of the difference between the two aliphatic hydrocarbon groups attached to the nitrogen atom is not critical, but is generally no more than 8 carbon atoms, and usually no more than 6 carbon atoms.

For the most part, the aliphatic hydrocarbon group is straight-chained or normal, and is attached to the amine nitrogen at an intermediate or terminal carbon atom.

Although it depends on the reaction conditions, it was found that when a molar ratio of amine and succinic anhydride of approximately 1:1 is used, a considerable amount of the amine remains unreacted as N, forming a salt of the produced succinamic acid.

In some cases, as much as 30% of the amine remains unreacted and significant amounts of salt are formed.

Thus, the salt often accounts for 1 of the total succiamide present.
It becomes 0 to 30 mol%.

Also, if a significant amount of water is present during the reaction process, this water can react with the succinic anhydride to form succinic acid.

If the temperature is not high enough to regenerate the succinic anhydride, the succinic acid will likely remain unreacted or form an amine salt with the available unreacted amine.

Therefore, one can conveniently reduce the mixture of succinic acid amide salts by not attempting to complete the reaction by simply using a molar ratio of amine to succinic anhydride of l:1, or by using a molar excess of amine. can be manufactured.

Amine salts can be easily obtained by adding an amine to a conveniently generated succinic acid amide or in an inert solvent.

The reaction can be facilitated by gentle heating.

The fuel compositions of the present invention contain a major amount of distillate petroleum fuel and about 0%
．． 0.005 to 3% by weight, preferably 0.01 to 1.0% by weight of the additive formulation according to the invention.

The additive formulation also contains about 0.3 to 10 parts by weight, preferably 0.3 to 10 parts by weight, preferably 0.3 to 10 parts by weight of component (B) or component (Q).
It consists of 5 to 5 parts by weight of the component or alkyl aromatic hydrocarbon.

Component (B) is an ethylene polymer, and component (C) is a succinamic acid derivative.

Concentrates of additive formulations containing 3 to 60% by weight of the above formulations in mineral oils, such as distillate fuel oils, may also be made.

The additive formulations of the present invention can be used alone as the only oil additive or can be used in conjunction with other oil additives such as corrosion inhibitors, antioxidants, sludge inhibitors, etc. .

In order that the present invention may be better understood, examples AE of additive formulations of the invention, examples A and B of fuel oils that may be used, examples A and B of flow tests and the additive formulations are provided below. Here is an example of how to use it.

Additive Formulation A-E Additive A--This is about 50% by weight light mineral oil and a melting point of about 72.
100 parts by weight of n-paraffin wax at 8°C with a chlorine content of approximately 1
It is a concentrate of about 50% by weight of wax-naphthalene, which is chlorinated to 2% by weight and condensed (Friedel-Krach) with about 8.8 parts of naphthalene.

Additive B - This is about 50% by weight light mineral oil and a melting point of about 51.
About 100 parts by weight of n-paraffin wax at a temperature of 7 to 53.9°C is chlorinated to give a chlorine content of about 14% by weight based on the weight of the chlorinated wax.
It is a concentrate of about 12 parts by weight of naphthalene and about 50% by weight of wax-naphthalene produced by Friedel-Krach condensation.

Additive C - It contains approximately 55% by weight light mineral oil, a number average molecular weight of approximately 1900 as determined by vapor pressure osmometer, and contains approximately 1.5 methyl end branches (vinyl acetate methyl groups) per 1000 molecular weight of the polymer. ethylene-vinyl acetate random copolymer containing about 38 weight percent vinyl acetate.

This copolymer was prepared by combining ethylene and vinyl acetate with dilauroyl peroxide in a cyclohexane solvent at a temperature of about 105°C.
Copolymerization was carried out under hydrogen pressure of about 73.815 ky/crA gauge pressure.

A typical laboratory preparation of this copolymer is as follows.

Add 1 cyclohexane to 31 autoclaves while stirring.
000 rfLl as a solvent, approximately 100 rfLl of vinyl acetate
Enter rIll.

The autoclave is then purged with 1 nitrogen followed by ethylene.

Next, autoclave at 105℃ while pressurizing ethylene.
and increase the pressure to about 73.815 kg/crA gauge pressure.

Next, the temperature is 105°C and the above 73.815 kg/
While maintaining crrt gauge pressure, add vinyl acetate to about 16
At 0.011111 hours, a solution consisting of 9% by weight dilauroyl peroxide dissolved in 91% by weight cyclohexane was added to about 8
Pump continuously into the autoclave at a constant rate of 01 rLl/h.

A total of 320ml of vinyl acetate and 111
2 dilauroyl peroxide is injected into the reactor.

After the peroxide injection is complete, the batch is held at 105° C. for an additional 10 minutes.

The temperature of the reactor contents is then lowered to about 60° C., the reactor is returned to atmospheric pressure, and the contents are removed from the autoclave.

Rinse one empty reactor with 11 g of hot benzene (approximately 50° C.) and add this benzene to the product.

The solvent and unreacted monomers were then stripped by bubbling nitrogen through the product overnight on a steam bath.

Other examples of polymers of this type are Canadian Patent No. 882.
No. 194.

For details on the determination of the degree of branching of this type of polymer, see Journal of Applied Polymer Science, Vol. 15, 1737-17.
42 (1971).

Additive 1 This is a concentrate containing about 60% by weight of chlorinated polyethylene with a number average molecular weight of about '5100 and a chlorine content of 21% by weight in mineral oil.

Additive E - This is a concentrate of about 35% mineral oil and about 65% active ingredients by weight, the active ingredients having (1) a molecular weight (by vapor pressure osmometer) of about 2000, a relative molar ratio of ethylene to isobutyl acrylate; 7:1 ethylene-isobutyl acrylate random copolymer and (2) U.S. Pat. No. 354
Succinamic acid prepared according to No. 4467, i.e. 1 molar amount of di-hydrogena
ted) tallow amine and the reaction product of 1 molar amount of alkenylsuccinic anhydride, the alkenyl group being an isomerized C15-20 monoolefin.

The weight ratio of the above copolymer and the above succinic acid amide is approximately 1:
It is 4.

Fuel Oils A and B Fuel A - This is a diesel fuel oil with a cloud point of -14
, 4°C, pour point -20.6°C, API specific gravity at 15.6°C 33.9, ASTM distillation test (D-86) 226.
It was 10% at 7°C and 95% at 329.3°C.

Fuel B - This is a diesel fuel oil and has a cloud point of -1
API specific gravity at 2.2℃ and 15.6℃ is 30.7. ;1'
AS TM-D-86 distillation test is 10 at 243.3°C.
%, 95% at 327.5°C.

Flow Tests A and B Flow Test A - In this test, a 200 rlll sample of oil is heated at a rate of -20,6C or -23,3C from a temperature of 5,6C above the cloud point of the oil at a rate of 2,2C/hour. At this temperature the oil was passed through a 270 mesh sieve with a diameter of ICrrL under a 91.44 CIrL (36") water column vacuum.

Record the % of sample passed in 25 seconds.

Flow Test B - This flow test was conducted in the same manner as Flow Test A except that a 30 mesh sieve was used.

Examples of the use of additive formulations - Various mixtures were prepared by simply adding and mixing the additives described above into the fuels described above, and were used to conduct flow tests A and B.

The special mixtures prepared and their cold flow properties are shown in the table below.

Table 1 Weight of additive in fuel A %y Recovery rate %, 27
0. ．． '7 Flow test using sieve A -20,6°C -23,5°C 0.4%A O-0,4
%C16- 〇, 2%C+0.2%A 100
-0.6%A0 0.6%CI2 0.5%A+0.1%C100 0.6%B O-0,3
%D 30 -0
,3%B+0.15%D 100
-0.5%A O-
0.25%A+0.15%D 100
-0.6%A0 0.15%E
00.2%A+0.06%E
100 none
O0 No. 2 Table - 12. Weight of additive in 30 meth fuel B at 2℃ % Fluid test using Tsuyu sieve
Recovery rate of experiment B %0.10%D
1000.075%D1 0.10%C100 0,075%C65 (1006%C3 0.20%B1 0.10%B+0.05%D 1000.10
%B+0.05%C91 None
0As is clear from Tables 1 and 2,
Blends according to the invention of wax-naphthalene lubricating oil pour point depressants (A and B) and ethylene backbone pour point depressants (C and D) or succinimide derivatives) are synergistic and wax The much smaller crystals (as measured by flow tests) improve the cold flow properties of atmospheric distillation fuels (i.e. atmospheric distillates) much more effectively than when a single component is used alone. I can see that it can be improved.

Claims (1)

[Scope of Claims] 1. An additive formulation for improving the low-temperature fluidity of distillate fuel oil, which comprises: (A) 8-point wax at about 37.8 to 933°C with a chlorine content of about 5 to 25% by weight; Friedel-Kraf condensation obtained by condensing a chlorinated wax with an aromatic hydrocarbon in a relative weight ratio of about 5 to 15 parts of the chlorinated wax to 1 part of the aromatic hydrocarbon. The product wax-aromatic hydrocarbon lubricating oil pour point depressant; (B) ethylene polymer chlorinated so that the chlorine content is about 5 to 35% by weight; ~C16 alpha monoolefin or a copolymer with a monoethyl unsaturated mono- or dialkyl ester having about 1 to 16 carbon atoms in the alkyl group at a molar ratio of 3 to 40, or H6 formula [in the above formula, R is a straight chain aliphatic hydrocarbon having 0 to 1 olefinic unsaturation, 14 to 40 carbon atoms, and attached to the succinyl group at the second carbon atom, X2 and X3 One of them is -NYY' (where Y
and Yl is an aliphatic hydrocarbyl group having 14 to 28 carbon atoms), and the other of X2 and X3 is hydrogen or an aliphatic hydrocarbon group having 1 to 30 carbon atoms, or It is an oxyaliphatic hydrocarbon having 1 to 30 carbon atoms, and Y2 and Y3 can form a 5- to 7-membered heterocyclic ring together with the nitrogen atom to which they are bonded. ] with a middle distillate fuel oil pour point depressant which is a succinamide derivative.