JPH03152191A - Additive for petroleum - Google Patents

Abstract

PURPOSE:To obtain the title additive for improving low-temperature fluidity of petroleum (product), containing a polymer comprising a mixture of lauryl acrylate and/or myristyl acrylate and another monomer as constituent units. CONSTITUTION:The aimed additive containing a polymer comprising (A) 95-30 pts.wt. mixed acrylate consisting essentially of a mixture of mainly lauryl acrylate and myristyl acrylate in a ratio of 90/10-40/60 and (B) preferably 2-8C monomer [e.g. olefin (derivative), ethylenic unsaturated carboxylic acid (derivative) or vinyl alcohol (derivative)] except the component A.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a petroleum additive, and more particularly, to a petroleum additive made of a specific acrylate polymer for improving the low-temperature fluidity of petroleum and petroleum products. Regarding additives.

[Conventional technology]

It is no exaggeration to say that petroleum is what keeps modern society functioning smoothly, and the various petroleum products obtained from petroleum. In particular, petroleum fuel oil is indispensable for the development of various industries and the advancement of motorization due to its convenience.

However, especially light oil and heavy oil, at low temperatures such as winter,
There is a problem in that the contained n-paraffin precipitates and the fluidity of the fuel oil decreases.

In the case of light oil, these n-paraffin crystals clog the fuel oil supply piping to the diesel engine and the filters along the way, making it difficult for the engine to run smoothly or, in some cases, causing the engine to stop. A similar phenomenon with heavy oil can also lead to problems such as stopping diesel engines on fishing boats and malfunctioning in boilers for greenhouse gardening.

In order to solve such problems, low-temperature fluidity improvers are used, but as a result of many years of research, the present inventors have
Patent No. 1418931, Patent No. 1449612, Patent 1
449615, patent number 1484158, etc., efforts have been made to solve these problems. These low-temperature fluidity improvers are very excellent as low-temperature fluidity improvers for light oil, and can efficiently improve low-temperature fluidity with a small addition amount.

[Problem to be solved by the invention]

However, it has been found that these additives have poor effects when added to heavy fuel oils such as heavy oil, and may not be able to efficiently improve low-temperature fluidity.

This is thought to be because heavy hydrocarbon substances contained in heavy fuel oil, which become unburned residual carbon during combustion, may interfere with the effects of these inventions.

The present invention provides a low-temperature fluidity improver that can improve the low-temperature fluidity of not only such heavy fuel oil but also all fuel oils and petroleum products.

[Means to solve the problem]

The present invention has (a) lauryl acrylate and myristyl acrylate as main components, and the ratio of lauryl acrylate to myristyl acrylate is 9071O to 40/6.
95-30% by weight of mixed acrylates that are 0 and (
b) A petroleum additive characterized by containing a polymer whose constitutional unit is 5 to 70% by weight of one or more monomers not included in the mixed acrylate. Further, in the present invention, a mixture with other low-temperature fluidity improving compounds not included in these compounds can also be used.

The fuel oil that is the subject of the present invention includes medium to heavy distillate oil obtained by directly distilling petroleum oil under normal pressure or reduced pressure; distillate oil that has been subjected to hydrodeflowing or catalytic reforming; thermal cracking, catalytic cracking; , Distillate oil that has been subjected to cracking treatment such as hydrocracking; Distillation residue when petroleum is distilled under normal pressure or reduced pressure; Distillation residue that has undergone hydrodesulfurization or catalytic reforming treatment; Thermal cracking, catalytic cracking ,
Distillation residues that have been subjected to decomposition treatments such as hydrocracking; extracts generated from lubricating oil manufacturing processes; asphaltic to resinous byproducts generated from various petroleum refining processes; fats and oils, fatty acids, alcohols, ethers, ketones, etc. Hydrocarbon compounds containing oxygen Polymerizable hydrocarbons such as niolefin and polyolefin; oil shale, oil sand, coal, etc., or their cracked oils; and one or two types selected from other hydrocarbon substances, etc. Hydrocarbon-based petroleum products are mainly composed of petroleum distillate oil and heavy oil, which are mixtures of the above.

The polymer of the present invention has (a) lauryl acrylate and myristyl acrylate as main components, and the ratio of lauryl acrylate to myristyl acrylate is 90/10 to
a mixed acrylate that is 40/60, and (b)
It is a polymer having a chemical structure obtained by copolymerizing one or more other monomers not included in this mixed acrylate, and is a mixture of one or more of these polymers.

The mixed acrylate constituting the polymer of the present invention is an ester mixture of a monohydric alcohol having a linear saturated hydrocarbon group and agrilic acid, and contains lauryl acrylate and myristyl acrylate as main components, and the ratio of lauryl acrylate to myristyl acrylate is 90/1 weight ratio
It is a mixed acrylate with a ratio of 0 to 40/60.

Further, as the monohydric alcohol having a straight-chain saturated hydrocarbon group, a corresponding hydrogenated reduction alcohol of a fatty acid is preferable, and synthetic alcohols having a similar straight-chain saturated hydrocarbon group can also be used.

Other monomers not included in the mixed acrylate constituting the polymer of the present invention are selected from olefins and their derivatives, ethylenically unsaturated carboxylic acids and their derivatives, vinyl alcohols and their derivatives, etc. One or more monomers containing 8 monomers are preferred.

Olefins and their derivatives include olefinic hydrocarbons such as ethylene, propylene, butene, isobutyne, pentene, hexene, heptene, octene, diisobutene, and styrene; isomerized olefins of these; di- to multimerized olefins; carbonyl groups, amino groups , cyano group,
Examples include olefinic compounds into which various derivative groups such as nitrile groups, hydroxyl groups, ether groups, and hydrocarbon groups have been introduced, and monomers having 2 to 8 carbon atoms are preferred.

Ethylenically unsaturated carboxylic acids and their derivatives include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and vinyl acetic acid; itaconic acid, crotonic acid,
Ethylenically unsaturated dicarboxylic acids such as maleic acid and fumarate; dimer of ethylenically unsaturated mono- and dicarboxylic acids.
Ethylenically unsaturated polycarboxylic acids such as polymers; ethylenically unsaturated carboxylic acid anhydrides; esters, ammonium salts, amine salts, amides and/or imides of ethylenically unsaturated carboxylic acids with alcohols, ammonia, amines, etc.; carbonyls There are ethylenically unsaturated carboxylic acid derivatives into which various derivative groups have been introduced, such as a group, an amino group, a cyano group, a nitrile group, a hydroxyl group, an ether group, a hydrocarbon group, etc., and monomers having 2 to 8 carbon atoms are preferable. .

Vinyl alcohol and its derivatives include vinyl alcohol; vinyl esters with various carboxylic acids; vinyl ethers with various alcohols;
Examples include vinyl alcohol derivatives into which various derivative groups such as amino groups, cyano groups, nitrile groups, hydroxyl groups, ether groups, and hydrocarbon groups have been introduced, and monomers containing 2 to 8 carbon atoms are preferred.

Especially preferred as other monomers not included in the mixed acrylate constituting the polymer of the present invention are those having relatively good copolymerizability with mixed acrylates such as methyl methacrylate, ethyl acrylate, and vinyl acetate, and having a small molecular weight. It is a monomer.

In the polymer of the present invention, lauryl acrylate and myristyl acrylate in the mixed acrylate constituting the polymer have very important functional roles, and their composition ratio is an essential element that characterizes the present invention. Similarly, other monomers constituting the polymer determine the overall structure of the polymer and are essential elements characterizing the present invention. Considering these points, a polymer in which mixed acrylate accounts for 95 to 30% by weight of all the monomers constituting the polymer, particularly a polymer in which 95 to 50% by weight is optimal.

The polymer of the present invention is produced by polymerizing the mixed acrylate described above and one or more other monomers by a conventional method such as emulsion polymerization, solution polymerization, or bulk polymerization; after polymerization, various monomers are added. Graft polymerization; After polymerization, various reactive compounds are reacted by addition, condensation, exchange, etc.; In the case of ester or amide monomers, after polymerization, all or part of the part is transesterified, amidated, or hydrated. Decomposition, etc.; After polymerization, ethylenically unsaturated carboxylic acid or its anhydride is esterified with alcohol, or amidated or imidized with ammonia or amine; After polymerization, it is subjected to various chemical or physical modifications; Polymerized products It can be obtained by a method such as mixing one or more of these. The molecular weight of the polymer is preferably 1,000 to 500,000, particularly 5,000 to 1
00000 is preferred.

Other low temperature fluidity improving compounds that can be used in combination with the polymers of the present invention include ethylene/saturated carboxylic acid vinyl ester polymers, ethylene/unsaturated carboxylic acid alkyl ester polymers, ethylene/olefin polymers, chlorinated polyethylene,
Chlorinated ethylene/vinyl acetate polymer, unsaturated carboxylic acid alkyl ester polymer, alkenyl succinic acid amide or its salt, chlorinated paraffin/naphthalene condensate, ester of nitrogen-containing compound having a hydroxyl group and saturated fatty acid,
Esters of polyhydric alcohols and saturated fatty acids, esters of polyoxyalkylene glycols and saturated fatty acids, esters of alkylene oxide adducts of polyhydric alcohols or partial esters thereof and saturated fatty acids, and these two.
There are mixtures of more than one species. In particular, JP-A-57-170
Estenope of a nitrogen-containing compound having a hydroxyl group and a saturated fatty acid as shown in No. 993 JP-A-57-170992
Ester of polyhydric alcohol and saturated fatty acid as shown in JP-A-57-177092, ester of polyoxyalkylene glycol and saturated fatty acid as shown in JP-A-61-181892. Preferred are esters of alcoholic hydroxyl group-containing compounds and saturated fatty acids, such as esters of alkylene oxide adducts of polyhydric alcohols or partial esters thereof and saturated fatty acids.

The present invention is a petroleum additive characterized by containing the above-mentioned polymer, or a petroleum additive characterized by using the polymer and another low-temperature fluidity improving compound in combination. A sufficient addition effect cannot be obtained unless the polymer and other low-temperature fluidity improving compounds are added in a total amount of 1 ppm or more by weight to the fuel oil, and preferably 5 to 50,000 ppm by weight or more.
Add ppm by weight.

The petroleum additive of the present invention can be used in combination with antioxidants, corrosion inhibitors, combustion aids, cleaning dispersants, anti-sludge agents, demulsifiers, etc. that are added to general hydrocarbon petroleum products. .

〔Effect of the invention〕

The petroleum additive of the present invention can dramatically improve the low-temperature fluidity of various hydrocarbon petroleum products, and does not adversely affect the properties of other petroleum products. There are significant advantages in the manufacture and use of products.

〔Example〕

Next, the present invention will be explained using inventive examples and comparative examples.

Table 1 shows the molecular weight and constituent monomer composition (wt%) of the polymer used. The number average molecular weight (MWn) and weight average molecular weight (MWw) were determined by gel permeation chromatography using a column packed with polystyrene packing and developed with tetrahydrofuran, using a calibration curve using a standard styrene with a known molecular weight. It is something.

Example I Light oil without additives of low-temperature fluidity improver conforming to JIS No. 220402 (clogging point knee: 5°C, pour point: -7.5°C)
) (hereinafter abbreviated as fuel oil 1), the above polymer was added, and the clogging point (JIS K 2288 > and pour point (J
Table 2 shows the results of measuring ISK 2269). Further, the amount added is shown in ppm by weight (the measuring method of the clogging point and pour point and the unit of the amount added are the same below).

From these results, it can be seen that all of the polymers that are petroleum additives of the present invention exhibit a very excellent effect of improving low-temperature fluidity as compared to the comparative example.

Example 2 In the same way, A heavy oil with no low temperature fluidity improver added that complies with JIS K 2205 Type 1 No. 1 (clogging point knee 6°C)
, pour point knee 10℃) (hereinafter abbreviated as fuel oil 2),
The measurement results of the clogging point and pour point when the polymer of the present invention was added are shown below.

Polymer type Addition amount 200 200 200 11 200 Clogging point Pour point (1) (1) -10-30 -12-32,5 -11-30 -12-32,5 From these results, the fuel of the present invention It is clear that the oil additive composition also exhibits an excellent low-temperature fluidity improving effect on Fuel Oil 2.

Example 3 Heavy oil C (pour point: 10°C) without additives of low-temperature fluidity improver conforming to JIS 2205 Type 3 No. 1 (hereinafter referred to as fuel oil 3)
The measurement results of the pour point when the polymer of the present invention was added to (abbreviated as ) are shown below.

Polymer Pour point type Addition amount (t') 1 1000 -7.5 1 2000 -20 1 5000 -32.5 From these results, it is clear that the fuel oil additive composition of the present invention It is also clear that the material also exhibits an excellent effect of improving low-temperature fluidity.

Example 4 The measurement results of pour point and clogging point when the polymer of the present invention and other low-temperature fluidity improving compounds (hereinafter abbreviated as compounds) were added to Fuel Oil 1 are shown below.

Compound 1 Nitrimethylolpropane tribehenate Compound 2: Polyoxyethylene (6 mol) Glycerin tribehenate Compound 3: Polyethylene glycol (molecular weight 600) Dibehenate Compound 4: Polyoxyethylene (5 mol) Sorbitan tribehenate polymerization Compound Clogging point Pour point type Addition amount Type Addition amount ('l:) (t)2 2
00 0 -9 -250 1
200 -13 -7.50 2 20
0 -12 -7.50 3 200
-11 -7.50 4 200 -1
1 -7.52 100 1 100
-12 -202 100 2 100
-11 -22.52 100 3 10
0 -10 -22.52 100 4
100 -10 -22.5 From these results, it is clear that when a polymer and a compound are used in combination, the clogging point is lowered better than when only a polymer is used.

Table 2 fuel oil 1 Additive effect on (light oil) Table 3 fuel oil 2 Additive effect on (heavy oil)

Claims (1)

[Claims] 1. (a) Mixed acrylate 95 to 95 containing lauryl acrylate and myristyl acrylate as main components and having a ratio of lauryl acrylate to myristyl acrylate of 90/10 to 40/60.
30% by weight, and (b) a polymer having, as a constituent unit, 5 to 70% by weight of one or more other monomers not included in the mixed acrylate. 2. The other monomer according to claim 1, which is selected from olefins and derivatives thereof, ethylenically unsaturated carboxylic acids and derivatives thereof, vinyl alcohol and derivatives thereof, and contains 2 to 8 carbon atoms. Additive for petroleum. 3. The petroleum additive according to claim 1, wherein the other monomer is vinyl acetate. 4. The petroleum additive according to claim 1, wherein another low-temperature fluidity improving compound is used in combination.