JPS6245692A - Additive for fuel oil and fuel oil with improved flowability - Google Patents

Abstract

PURPOSE:To improve the flowability and clogging properties of a fuel oil, by mixing an intermediate distilled fuel oil having a narrow boiling range with a particular ethylene copolymer. CONSTITUTION:A fuel oil is blended with the following copolymer I or copolymer I and copolymer II in an amt. of 10-2,000ppm by weight based on the fuel oil. The copolymer I comprises ethylene and at least one member selected from among vinyl monomers contg. a 5-7-membered ring having nitrogen in its molecule and copolymerizable with ethylene and (meth)acrylamide derivative. The copolymer II comprises ethylene and at least one member selected from among vinyl esters of satd. carboxylic acids or ethylenic unsatd. mono-or dicarboxylic acids or their esters of the formula [wherein R1 is H or a methyl group; R2 is OOCR4 or COOR4 (wherein R4 is H or a 1-18C alkyl); and R3 is H or COOR4].

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to an additive for fuel oil, particularly an additive having a boiling point range of 12
A middle distillate fuel oil having a temperature of 0 to 500°C, and 2
The present invention contains an additive for improving the clogging property at low temperatures of a fuel oil having a narrow boiling point range in which the difference between the 0% distillation temperature and the 90% distillation temperature is less than 100°C, and the additive. This invention relates to fuel oil with improved fluidity.

[Prior Art] When the above-mentioned fuel oil is exposed to low temperatures, the wax content in the oil precipitates as crystals, which causes clogging in the transitor when used as fuel for a diesel engine. This can cause engine malfunction, or in severe cases, it can solidify in the fuel pipe and stop flowing at all.

In order to solve these problems, various wax crystal modifiers that interact with wax crystals have been proposed. As such a crystal modifier, for example, a copolymer of low-molecular ethylene and a single ethylenically unsaturated ester is disclosed in Japanese Patent Publication No. 48-23185, and a copolymer of low-molecular ethylene and an ethylenically unsaturated ester is disclosed in Japanese Patent Publication No. 55-33480. Synergistic flow number N compositions comprising a component serving as a nucleating agent and a component serving as a crystal modifier of the same copolymer are also disclosed in JP-A-59-53594, JP-A-59-8790, and JP-A-59-8790. Open 11i156-3E1588
Each of the publications teaches the use of the same copolymer in combination with various surfactants. However,1 these proposed improvers have a difference of 10% between the 20% distillation temperature and the 90% distillation temperature.
Effectively improves clogging and fluidity for middle distillate oils with a wide boiling point range above 0°C, but the temperature difference is +00°C.
For middle distillate fuel oils with a relatively narrow boiling range of +-7.0° C., the fluidity can be improved, but the clogging property is not improved.

Gas oil is a typical middle distillate fuel oil with a narrow boiling point range. In order to improve the clogging properties of such gas oils, it is currently common practice to mix them with a kerosene fraction, which is a lower boiling point fraction. However, such a method is not only disadvantageous in terms of cost, but also leads to a decrease in the yield of kerosene, and is not an industrially advantageous method.

[Problems to be Solved by the Invention] Under these circumstances, if an effective improving agent for improving the clogging property of gas oil with a narrow boiling point range could be created, it would have great industrial value.

In view of these current circumstances, the inventors of the Woodworks have carefully considered solutions to this problem, and found that middle distillate oils with a narrow boiling point range are exposed to low 1- When wax crystals precipitate in the workpiece, the temperature difference between the temperature at which the crystals begin to precipitate (cloud point) and the temperature at which they clog or solidify (low temperature filtration clogging point or pour point) is extremely small, and the crystals in the workpiece are It was discovered that the crystallization rapidly progresses as soon as precipitation begins, leading to solidification of the oil. From this, 1
The present inventors have discovered that the phase between wax and fluidity improver! We believe that the delicate balance between the fluidity improver's solubility in oil and its ability to modify wax crystals is more important in the f effect.
As a result of manufacturing and studying various copolymers, we focused on developing a fluidity improver that effectively acts not only on middle distillate oils with a wide boiling point range, but also on middle distillate oils with a narrow boiling point range. ,
The present invention has been achieved.

[Means for Solving the Problems] That is, the first invention of the present invention is based on 5~? containing (a) ethylene and (b) nitrogen. Contains a copolymer (I) containing a C1 ring in the molecule and consisting of at least one monomer selected from vinyl monomers, acrylamide derivatives, and methacrylamide derivatives copolymerizable with ethylene. The present invention provides a fuel oil additive with special characteristics.

The second invention in the present invention is.

Together with the above copolymer (I), (a) ethylene and (e) the general formula (wherein R1 represents hydrogen or a methyl group, and R2 represents 10
0CRa group or -(:OOR, group (in the formula, R4 is hydrogen or an alkyl group having 1 to 18 carbon atoms),
R3 is hydrogen or a -GOOR4 group. ) A copolymer (II) consisting of at least one vinyl ester of a saturated carboxylic acid or an ethylenically unsaturated carboxylic acid or dicarboxylic acid or an ester thereof.
It is a fuel oil additive characterized by containing.

In addition, unreleased I is a mixture of the copolymer (I) or the copolymer (II) described in 111j above.
Contains 1θ to 2000 ppm based on oil.

A third invention provides a fuel oil with improved fluidity.

The additive of the present invention is applicable to middle distillate fuel oils with a boiling point range of 120 to 500°C, and not only to fuel oils with a difference between 20g distillation temperature and 90% distillation temperature of 100°C or more, but also to this distillate fuel oil. It also works effectively on fuel oil with a temperature difference of 100°C or less, improving fluidity and clogging properties.

Ethyl copolymer (I) and (I) used in the present invention
II) is defined as follows.

Copolymer (I) first J(?, aggregate I), (a) ethylene and (b
) At least one type of elit compound (hereinafter referred to as tlL mer (b)) selected from vinyl ELIT derivatives, acrylamide derivatives, and methacrylamide derivatives that contain 5 to 71 nitrogen-containing rings in the molecule and are copolymerizable with ethylene. It is a copolymer consisting of

! -N body (b) is specifically, for example, N-vinyl-2-
pyrrolidone, N-vinylpyrrolidine, N-vinylviroline, vinylpyridine, vinylquinoline, N-vinylphthalimide, N-vinylimidazole, N-vinylcarbazolesamethyleniminoethyl methacrylate, acrylamide, methacrylamide, N,N-dimethylacrylamide, N , N-dimethylmethacrylamide, N-methylolacrylamide, and the like.

The composition of copolymer (I) is that ethylene (a) is 75 to 99
mol 2, monomer (b) is 25 to 1 mol 2, preferably 2
The amount is 0 to 3 moles, more preferably 18 to 7 moles. Further, the molecular acid of copolymer (I) has a number average molecular weight of 5
00 to ioooo, preferably 500 to 5000.

The second copolymer (rI) is composed of (a) ethylene and (c) the general formula (wherein R1 represents hydrogen or a methyl group, and R2 represents 10
0C: Ra or -COORa (in the formula, R4 is hydrogen or an alkyl group having 1 to 18 carbon atoms);
RB Lshi hydrogen mata it -GOOR. ,! It's a melon. ) A copolymer consisting of at least one type of vinyl ester or ethyl unsaturated carboxylic acid or dicarboxylic acid or its ester (hereinafter referred to as monomer (c)) of a saturated carboxylic acid represented by be.

Specifically, vinyl acetate, vinyl propionate, vinyl acetate, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, stearyl acrylate, methacrylic acid, Methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, lauryl methacrylate, stearyl methacrylate, dimethyl maleate, diethyl maleate, dipropyl maleate, diethyl fumarate.

These include diethyl fumarate and dipropyl fumarate.

The composition of copolymer (II) is that ethylene (a) is 75 to 3
9 moles 2. The monomer (c) represented by the above formula (A) is 25
~1 mole2. Preferably it is 20 to 3 moles2, more preferably 18 to 7 moles2. In addition, copolymer (II)
The number average molecular weight of is 500 to 10,000, preferably 500 to 5,000.

Component (a) of these copolymers (1) or copolymers (
Component (c) in 11) interacts with wax 1■1. It greatly affects the solubility in oil and the dispersibility of the precipitated workpiece, and the composition content in each copolymer is preferably 3 to 20 mols, more preferably 7 to 18 mols, as described above.

In addition, the molecular weight of copolymer (I) (n) is closely related to solubility in oil and workability during handling, and is between 500 and 5000.
is preferred.

Even when used alone, the copolymer (I) of the present invention acts effectively on fuel oils with a narrow boiling point range, but due to cost considerations, it is combined with the second copolymer (II). Mixing is advantageous.

The mixing ratio is O to 99 parts by weight of copolymer (II) to 100 to 1 part by weight of copolymer (I). Preferably copolymer (IT) to 85 to 15 parts by weight of copolymer (I)
It is 15 to 85 tons.

When the copolymers (1) and (II) of the present invention are used as a fluidity improver for fuel oil, the weight ratio of the copolymers (1) and (II) to the fuel oil is 10 to 2000 pp, preferably 100 to 1000 pp.
It is added within the PP layer.

In addition, when using a mixture of two types of copolymers, each copolymer can be added directly to the oil separately, but a common solvent for both, such as kerosene, aromatic solvent, or cellosolve, can be used. Preferably, it is added in the form of a dissolved concentrate at a concentration of 10-5 oz.

The copolymers of the present invention can be used alone as a single additive or, if necessary, with other additives, such as other pour point depressants, rust inhibitors, antioxidants, water separating agents, anti-sludge agents, etc. It is also possible to use it in combination with other agents.

The copolymer of the present invention is produced by subjecting predetermined monomers to copolymerization conditions, and can be produced using a high-pressure polyethylene production apparatus.

l) Catalyst The copolymer of the present invention is produced by radical polymerization. Accordingly, the catalysts used in the preparation of the copolymers of the present invention are compounds that photogenerate free radicals.

For example, oxygen, dialkyl peroxide such as di-t-butyl peroxide, t-butylcumyl peroxide, diacyl peroxide, diacyl peroxide such as acetyl peroxide, l-butyl peroxide, octanoyl peroxide, etc. peroxydicarbonates such as i-propyl peroxydicarbonate and di-2-ethylhexyl peroxydicarbonate;
Peroxy esters such as t-butyl peroxyisobutyrate, t-butyl peroxy bivalate, t-butyl peroxy laurate, ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 1.1-bis-t - Peroxyketals such as butylperoxycyclohexane and 2,2-bis-t-butylperoxyoctane, hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide, 2,2-azobisisobutyro Azo compounds such as nitriles.

2) Tamasha This polymerization is preferably carried out in a continuous manner. The first reactor is a continuous stirring tank type reaction atmosphere or a continuous hole tube type reaction atmosphere, which is commonly used in high-pressure radical polymerization of ethylene. equipment can be used.

The polymerization can be carried out as a single-zone process using these single reactors, but it can also be carried out using many reactors connected in series, possibly using condensers in series, or in multiple zones. It is also possible to use a single reactor, the interior of which is effectively divided into several zones. In a multi-zone process, the monomer concentration is controlled in each reactor or reaction zone in such a way that the reaction conditions in each zone are varied to control the properties of the polymer obtained in each reactor or reaction zone. It is common to include body composition, catalyst concentration, molecular weight regulator concentration, etc. in the iA section. When using multiple reactors in series, use 2 or more seed reactors or 2! ! In addition to the combination of i or more tubular reactors, it is also possible to use a combination of one or more seed reactors and one or more tubular reactors.

The polymer produced in the reactor or reactors can be separated from unreacted monomer and processed as in the production of conventional high pressure polyethylene. The mixture of unreacted monomers is mixed with an additional amount of the same monomers,
Repressurize the reactor to ring. The additional amount of monomer added as described above is of a composition that returns the composition of the mixture to that of the original feed, and generally this additional amount of monomer is added to the polymer separated from the polymerization vessel. The reactor in this case is preferably a seed type reactor in order to obtain a copolymer having a uniform composition, which has a composition approximately corresponding to the composition of the copolymer.

The catalyst is usually dissolved in a solvent with a small chain transfer effect and directly injected into the reactor using a high pressure pump.

The concentration is preferably about 0.5 to 30% by weight or about 14%.

Suitable solvents include, for example, hexane, heptane, white spirit, hydrocarbon oils, cyclohexane, toluene, higher branched chain saturated fatty acid hydrocarbons, and mixtures of these liquids.

In high-pressure radical polymerization, a chain transfer agent is generally used to adjust the molecular weight, except in special cases.

As the chain transfer agent, all those used in normal high-pressure radical polymerization can be used.6 For example, alkanes such as ethane, propane, butane, hexane, heptane, propylene, etc.
Alkenes such as butene and hexane, alcohols such as ethanol, methanol and propatool, ketones such as acetone and methyl ethyl ketone, aldehydes such as acetaldehyde and propionaldehyde, and many other chain transfer agents used in high pressure methods can be used. .

The gaseous chain transfer agents are injected into the suction side of the compressor, and the liquid ones are pumped into the reaction system.

2) Polymerization conditions (a) f#, combined pressure The polymerization pressure employed is a pressure exceeding 500 kg/cm, preferably 1000 to 4000 kg/C11
The range is 5.

(b) Polymerization temperature The polymerization temperature is at least 120°C, but preferably
It is in the range of 150 to 300°C.

3) In addition, the copolymer of the present invention produced in the reactor is separated from the monomer by separation etc. according to the conventional method of high-pressure radical polymerization method,
It becomes a product as it is. This product may be used as is, or may be subjected to various post-treatment steps such as those already used for products obtained by high-pressure radical polymerization.

[Example] The measurement method used for quality evaluation of the copolymer used in the present invention is as follows.

l) Molecular weight By gel permeation chromatography.

2) Comonomer content: By elemental analysis method and IR method.

3) Cold Filter Pl
uggingPoint, abbreviated as CFPP):
Conforms to British standard IP-309.

4) IIi, Pour Point (abbreviated as PP): According to JIS K-2289.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Production examples of various copolymers used in Examples of the present invention are shown below.

Production Example 1 (Copolymer Ia) Using a stirring autoclave type continuous reactor with an internal volume of 1.5 Q, ethylene was 32 kg/hr and hexamethyleneiminoethyl methacrylate (HMiMA) was 500 kg/hr.
g/I! A solution dissolved in ethyl acetate in the ratio of e, i
c/hr, a solution of propionaldehyde dissolved in ethyl acetate at a ratio of 500 g/(!) was 8.8 Q,/br,
and t-butylperoxyisobutylene 1/- as a catalyst.
A solution prepared by dissolving 15 g of 10 parts in deuterated hexane is 0.501! ,/hr [7, polymerization pressure 1500 kg/cm2. A copolymer was produced at a polymerization temperature of 220°C. The obtained copolymer Ia has a molecular weight of 120
0, HM i HA containing II matχ.

Production Example 2 (Copolymer Ib) Copolymers with different grade indexes were produced in the same manner as in Production Example 1.

Ethyl 7 32kg/hr, HMiMA 500g/
Q-ethylene acetate solution at 4.9 Q,/hr, propionaldehyde 500 g/Q-ethylene acetate solution at 1.5 Q,/hr, and t-butylperoxyisobutyrate 15 g/(!, -n −
0.440% hexane solution. / hr, and the polymerization pressure was 1500 kg/c+s2. A copolymer was produced at a polymerization temperature of 220°C. The resulting copolymer Ib has a molecule of M3300. Including HMiMA (i7.5
There was mol$te.

Production Example 3 (Copolymer Ic) In the same manner as in Production Example 1, the comonomer was converted to tovinyl-2-
-Cj (polymer was produced) by changing to pyrrolidone.

32 kg/hr of Edin 1/ton, 200 g of N-vinyl-2-pyrrolidone (MVP)/14.91 g of Q-acetic acid ethylene solution. /hr, propionaldehyde 500g
/N-acetic acid ethylene solution 4.51! , /hr, and t-butylperoxyisobutyre as catalyst) 15
g/12-n-hexane solution at 0.4 (1,,/h
The polymerization pressure was 1500 kg/
Cm2. A copolymer was produced at a polymerization temperature of 220°C. The obtained copolymer rc has a molecular weight of 2200 and an NVP content of i10.
+mol$.

Production Example 4 (Copolymer ITa) A copolymer was produced in the same manner as in Production Example 1 except that the comonomer was changed to vinyl acetate.

Ethylene at 32J/hr, vinyl acetate (vA) at 18Q
12
0 g/Q, -n-hexane solution Q, 6 Q,/
hr, and the polymerization pressure was 1500 kg/hr.
A copolymer was produced at Cm2 and a polymerization temperature of 200°C.

The obtained copolymer ■δ has a molecular weight of 3300 and a VA content of 13.
5OLS 't' h.

The fuel oils used in the following examples were fuel oil A with a wide boiling point range and fuel oil B with a narrow boiling point range, and their properties were as shown in Table 1.

Table 1 Examples 1 to 5 and Comparative Example 1 The copolymers of Production Examples 1 to 4 and their mixtures were dissolved in kerosene to give a weight-M ratio of 3 (H). The copolymer was added to fuel oils A and H shown in Table 1 so that the hair amount ratio was 150 ppm, and the wave point (pp) was
and the low temperature filtration clogging point CC (FPP) were measured. The results are shown in Table 2.

Table 2 [Operations and Effects] As is clear from the results shown in Table 2, the additive of the present invention has a 2(H Distillation temperature and 90! The difference between distillation temperature is 1
Not only fuel oil A below 00℃, but also this distillation temperature difference of 1
It also works effectively on fuel oil mills at temperatures below 00°C, improving the undulation properties of fuel oil and significantly improving clogging properties.

Claims (3)

[Claims] (1) At least one monomer selected from (a) ethylene and (b) a vinyl monomer, an acrylamide derivative, or a methacrylamide derivative that is copolymerizable with ethylene and which contains a 5- to 7-membered ring containing nitrogen in its molecule. A fuel oil additive characterized by containing a copolymer (I) consisting of (2) At least one monomer selected from (a) ethylene and (b) a vinyl monomer, an acrylamide derivative, or a methacrylamide derivative that is copolymerizable with ethylene and which contains a 5- to 7-membered ring containing nitrogen in its molecule. Copolymer (I) consisting of (a) ethylene and (c) general formula ▲ Numerical formula, chemical formula, table, etc. ▼ {In the formula, R_1 represents hydrogen or a methyl group, R_2 represents -OOCR_4 group or -COOR_4 group (R_4 in the formula
is hydrogen or an alkyl group having 1 to 18 carbon atoms. )
and R_3 is hydrogen or a -COOR_4 group. } A fuel oil additive characterized by containing a copolymer (II) consisting of a vinyl ester of a saturated carboxylic acid or an ethylenically unsaturated mono- or di-carboxylic acid or at least one ester thereof. . (3) At least one monomer selected from (a) ethylene and (b) a vinyl monomer, an acrylamide derivative, or a methacrylamide derivative that is copolymerizable with ethylene and which contains a 5- to 7-membered ring containing nitrogen in its molecule. A copolymer consisting of
I ), or the copolymer (I) and (a) ethylene and (c) general formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ {In the formula, R_1 represents hydrogen or a methyl group, R_2 represents -OOCR_4 group or -COOR_4 group (R_4 in the formula
is hydrogen or an alkyl group having 1 to 18 carbon atoms. )
and R_3 is hydrogen or a -COOR_4 group. } A copolymer (II) consisting of at least one vinyl ester of a saturated carboxylic acid or an ethylenically unsaturated mono- or di-carboxylic acid or an ester thereof represented by Contains fuel oil with improved fluidity.