JPS59124994A - Fuel composition - Google Patents

Abstract

PURPOSE:To improve low temperature stability of fuel, by adding an oxyalkylene group-containing vinyl copolymer to a fuel consisting of a mixture of two or more of water and/or alcohol, solid hydrocarbon and liquid hydrocarbon. CONSTITUTION:Fuel is prepared by blending at least two of water and/or alcohol, solid hydrocarbon (e.g. coal) and liquid hydrocarbon (e.g. gas oil) and an oxyalkylene group-containing vinyl copolymer is added to the fuel to obtain the aimed fuel composition. Preferred vinyl copolymer is one obtained by copolymerizing (A) a monomer having an oxyethylene group of the formula (where n is 1-100) (e.g. polyoxyethylene acrylate), (B) a vinyl ester of a lower aliphatic saturated carboxylic acid and (C) a hydrophobic group-containing vinyl monomer (e.g. vinyl acetate).

Description

DETAILED DESCRIPTION OF THE INVENTION Hydrocarbon mixtures have various combinations of compounds, and their uses are wide-ranging, with fuel being a typical example. For example, a small amount of methanol may be mixed into the core to improve the combustion efficiency of heavy oil and expand its application to light oil or medium oil fields, or fine powder may be used to transport fine coal safely and efficiently. Practical applications are expected, such as by dispersing it in water, methanol, or hydrocarbon oil. However, in any application, it is necessary to add various surfactants to maintain the stability of the hydrocarbon mixture so that phase separation does not occur. It has been proposed that vinyl polymers such as partially saponified products, ethylene-vinyl acetate copolymers, or their gunned products can be used as suitable stabilizers.

However, when this stabilizer is used, there is a risk that the dispersion state will be destroyed and phase separation will occur during storage in winter or handling in cold regions 1 due to poor storage stability at low temperatures. I was disappointed that there was room for improvement.

However, the present inventors have proposed that B) water and/or alcohol, (
T → solid hydrocarbon, Q) selected from liquid hydrocarbons (
When blending a vinyl copolymer having an oxyalkylene group, preferably a hydrophobic group, into a hydrocarbon mixture consisting of a combination of at least two of (a), (b), and (c): 1. The present invention has been completed with the novel effect of providing a fuel composition with excellent stability at low temperatures.

As mentioned above, the stabilizer used in the present invention has an oxyalkylene group in the vinyl copolymer, and by introducing such a specific functional group, it exhibits performance that far exceeds that of conventional stabilizers. It is.

Moreover, the copolymer containing the oxyalkylene group must be a vinyl copolymer, and even if it contains the group, other than vinyl copolymers such as polyalkylene glycol may be used as a stabilizer. Even if 7 is used, the effect of the present invention cannot be obtained at all. The above-mentioned oxyalkylene group may be present in the main chain, side chain, or terminal in the copolymer, and the stabilizing effect is particularly exhibited when it is present in the side chain.

Although the polymer can be prepared by any method, homopolymerization of a monomer containing an oxyalkylene group poses practical problems in terms of the polymerizability of the monomer or the physical properties of the resulting polymer. Therefore, the vinyl polymer referred to in the present invention essentially means a copolymer of this monomer and another vinyl monomer, and a vinyl monomer containing an oxyalkylene group is It can be produced by copolymerization or graft polymerization with other vinyl monomers, or by post-reacting a pre-prepared vinyl polymer with an oxyalkylene. In any case, it is preferable to have an oxyalkylene group in the side chain. From the physical properties of the stabilizing effect, the manufacturing aspect, and the nesting part of the raw material, the oxyalkylene group-containing vinyl monomer [hereinafter abbreviated as component A] is used.
The vinyl monomer to be copolymerized with is vinyl ester of lower aliphatic saturated carboxylic acid (e.g. vinyl formate, vinyl acetate, etc.) or lower alkyl ester of ethylenically unsaturated carboxylic acid (e.g. methyl (meth)acrylate, (meth) ) ethyl acrylate, ethyl maleate, methyl maleate, etc.) [hereinafter referred to as component (B)] is the most practical.

Furthermore, in the present invention, when a copolymer obtained by coexisting a hydrophobic group with the vinyl copolymer containing the above-mentioned oxyalkylene and M is used as a stabilizer, an even more excellent effect is exhibited. Hydrophobic groups and oxyalkylene groups are present in the side chains of vinyl iron cars and copolymers.For example, the copolymer is good for each component forming a hydrocarbon mixture, that is, hydrocarbons, alcohols, and water. Because of this affinity, the dispersion stability of hydrocarbon mixtures is significantly improved. In this case, the presence of component (B) is not necessarily required as long as the oxyalkylene group and the hydrophobic group are present in the copolymer.

The reason why such an effect can be obtained is that no matter how the type or composition of the target hydrocarbon mixture changes,1, by adjusting the type and content of the oxyalkylene group and the hydrophobic group, the This is because a vinyl copolymer that can exhibit the best dispersion stabilizing effect can be easily produced.

Such polymers can be produced by any method, e.g.
A method of copolymerizing or graft polymerizing a vinyl monomer containing an oxyalkylene group and a hydrophobic group in the same molecule with component (B), a method of copolymerizing or graft polymerizing a vinyl monomer containing a hydrophobic group in the same molecule; Methods include producing a polymer containing an oxyalkylene group and reacting it with an oxyalkylene, and producing a polymer containing a vinyl monomer containing an oxyalkylene group as one component and introducing a hydrophobic group into the polymer. However, from the viewpoint of ease of production, raw material acquisition, etc., the above-mentioned (5) oxyalkylene group-containing vinyl monomer and (B) vinyl ester of lower aliphatic saturated carboxylic acid and/or ethylenic acid are usually used. It is advantageous to copolymerize a lower alkyl ester of an unsaturated carboxylic acid and a hydrophobic group-containing vinyl monomer (hereinafter abbreviated as component (C)).

Next, the monomers used for producing the stabilizer used in the present invention will be explained.

The oxyalkylene group in the present invention is an alkyl group of the general formula, X is hydrogen, an organic residue such as an alkyl group, an alkyl ester group, an alkylamido group, a sulfonic acid group, m is O or 1, and n is an integer from 1 to 100. (integer)].

Although X is usually hydrogen, the type of X has little to do with the performance of the stabilizer, and it is the number of n that has the most influence on the performance. The number of n is advantageously 1 to 5°, preferably 6 to 5
About 0 oxyalkylene groups are practical, and polyoxyethylene groups, polyoxypropylene groups, polyoxybutylene groups, etc. are effective.

(5) Examples of the vinyl monomer having an oxyalkylene group include the following, but the present invention is not limited to these.

[where R is hydrogen or methyl group, human is alkylene group, substituted alkylene group, phenylene group, substituted phenylene group, l is 0 or an integer of 1 or more, m is 0 or 1, n is 1
~100 integer], polyoxyethylene (meth)
Examples include acrylate, polyoxypropylene (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and the like.

3 [wherein R3 is hydrogen or an alkyl group or the same as above], polyoxyethylene (meth)acrylamide, polyoxypropylene (meth)acrylamide, N-methylol (meth)acrylamide , N-
Examples include methylol (meth)acrylic acid amide, polyoxyethylene (1-(meth)acrylamide-1,1-dimethylglobil) ester, and the like.

[R, R1, R2, m, and n are the same as above], such as polyoxy-ethylene (meth)allyl ether, lyoxypropylene (meth)allyl ether, and the like. In addition, (meth)allyl alcohol itself can also be used.

[:A, R1, R2, JXrn, n are the same as above], such as polyoxyethylene vinyl ether and polyoxypropylene vinyl ether.

(B) Vinyl esters of low aliphatic saturated carboxylic acids include vinyl formate and vinyl acetate, and lower alkyl esters of ethylenically unsaturated carboxylic acids include methyl (meth)acrylate, ethyl (meth)acrylate, Methyl maleate, ethyl maleate, methyl crotonate, ethyl crotonate, ethyl itaconate, ethyl itaconate, methyl sorbate, ethyl sorbate, and the like are used.

These can be used individually or in combination.

In addition, in the case of copolymers using vinyl formate and vinyl acetate,
This component may be partially saponified.

(C) The hydrophobic group in the hydrophobic group-containing vinyl monomer refers to an alkyl group having 6 or more carbon atoms, a substituted alkyl group, or an aryl group. Examples of hydrophobic group-containing monomers that can be used in the present invention are given below, but the present invention is not limited to these.

-71 艧ノ≦之' and 1152 steps made in one day = vinyl propionate, vinyl acetate, vinyl caprate, vinyl lacrylate, vinyl persate, vinyl palmitate, vinyl stearate, etc.

Alkyl vinyl ether probyl vinyl ether, butyl vinyl ether, hexyl vinyl needle, octyl vinyl ether, tesyl vinyl ether, dodecyl vinyl ether, tetradecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, etc.

1γノ￥7ya, -sky, -Lsu. 1 stone - 2 years old ≧ -
-propyl allyl ether, butyl allyl ether,
Hexyl allyl ether, octyl vinyl ether, decyl allyl ether, dodecyl allyl ether, tetradecyl allyl ether, hexadecyl vinyl ether,
Octadecyl allyl ether etc.

Danto,,,,Setan Pressure Resistant C, Midori Hayako 5, Toshiba Koba, 4L Shigo' Zoan (meth)propyl acrylate, (meth)acrylate butyl, (meth)acrylate pentyl, (meth)acrylate hexyl , (meth)heptyl acrylate, (meth)octyl acrylate, (meth)decyl acrylate, (meth)acrylate
Hexadecyl acrylate, octadecyl (meth)acrylate, and others, monoalkyl maleate, dialkyl maleate, alkyl crotonate, algyl icconate, alkyl besorbic acid ester, alkyl oleate, etc.

1--Bukuri-jy /L/M:/W
F) - Should Lee□tv x□-x 7-, IL
/ - = allyl stearate, allyl lafric acid, allyl coconut oil fatty acid, allyl octylate, allyl butyrate, etc.

1, -a 4 cony 1-2m, -,'=propylene, α-hexene, α-octene, α-decene, α-dodecene, α-hekyladecene, α-octadecene, etc.

Other materials such as styrene and alkylamino (meth)acrylate can also be used. These hydrophobic group-containing monomers may be used alone or in combination of two or more.

C. Although not an essential component, it is also possible to copolymerize a small amount of monomers containing polar groups such as carboxylic acids such as (meth)acrylic acid, crotonic acid, maleic acid, and itaconic acid, or their amides and salts. It is.

The composition ratio of the vinyl copolymer used in the present invention varies somewhat depending on the type and composition of the target hydrocarbon mixture, but usually in the case of a copolymer consisting of (N, 0) components, (N is 0.
5 to 95 mol%, preferably 1 to 90 mol%, (N
, CB), in the case of a copolymer consisting of components (C), (A)
is 0.01 to 95 mol%, preferably 0.1 to 90 mol%
, (B) is 0.1 to 95 mol%, preferably 0.5 to 90
mol%, (C) is 0.01 to 95 mol%, preferably 1 to 95 mol%
It is 90 mol%.

The amount of the vinyl copolymer used in the present invention varies somewhat depending on the type of target mixture or its purpose, so it cannot be unconditionally defined, but it is usually 0.00% based on the entire composition.
A range of 5 to 5% by weight is suitable. The polymer is in powder form,
It can be added in either block or solution form.

In non-invention, the length has an average degree of gunning of 95 mol% or less,
When a polyvinyl acetate resin having an average degree of polymerization of 1500 or less is used in combination, stability is further improved.

Among the above polyvinyl acetate resins, the average saponification degree is 90.
Particularly effective are polyvinyl acetate partially saponified products having an average degree of polymerization of 50 to 1000, ie, a partially saponified product having a low degree of gunning and a low degree of polymerization.

In addition to the vinyl acetate group and the hydroxyl group, a small amount of other functional groups may be included in the molecule of the polyvinyl acetate resin.

Further, the polyvinyl acetate resin can be added in any form of powder, block, or melted form, and as a solution, it can be added in an aqueous solution, a methanol solution, a methanol solution, a methanol/methyl acetate solution, etc. An alcoholic solvent solution is suitable, and it is of course possible to use water and other solvents that are compatible with the alcohol in combination, if necessary.

The amount of the resin to be added also varies depending on the type of the target liquid mixture or its purpose, so it cannot be absolutely specified, but it is usually in the range of 0.005 to 5% by weight based on the entire composition. 5% of the polyvinyl acetate resin to the copolymer
The effect is particularly remarkable when used in combination with ~90% by weight.

In the present invention, methanol is typically used as the alcohol, but higher alcohols such as ethanol, propatool, and butanol can also be used. Examples of solid hydrocarbons include coal, asphalt, coal tar, and pitch. Furthermore, liquid hydrocarbons include gasoline (for automobiles and aviation), jet fuel oil, heavy oil, light oil, and heavy oil (A
Heavy oil, B heavy oil, C heavy oil), lubricating oil, etc. are exemplified, but according to the present invention, remarkable effects can be obtained particularly for hydrocarbons having a boiling point of 200'C or higher.

The hydrocarbon mixture to which the present invention is applied is selected from (a) water, alcohol, or water/alcohol, (b) solid hydrocarbons, and (c) liquid hydrocarbons.
Any combination of two or more of c) may be used.

Preferred combinations from a practical standpoint include gasoline/methanol, diesel oil/methanol, heavy oil/methanol, coal/ethanol, coal/ethanol, asphalt/methanol, coal/water, asphalt/water, etc. Light oil/methanol, heavy oil/methanol, or asphalt/methanol are particularly effective. The mixing ratio in the mixture is not particularly limited and may be selected from any range depending on the purpose. For example, when methanol is mixed with heavy oil, ethanol of 50% by weight or less is practically used.

When preparing a Zero-Hatsu-1 composition, there are no restrictions on the mixing method; in short, water, alcohol, solid hydrocarbons, liquid hydrocarbons, and copolymers or polyvinyl acetate resins may be mixed under stirring. do it. The order of addition is arbitrary.

Further, during such operations, arbitrary compounds such as various additives such as various surfactants and combustion aids may be used in combination as necessary.

The composition thus obtained has excellent stability, even when stored at low temperatures for a long period of time, and has appropriate fluidity, making it useful as a fuel.

Hereinafter, the present invention will be specifically explained with reference to examples. Parts or percentages are standard unless otherwise specified.

Examples 1 to 6 100 parts of light oil was charged into a stainless steel vessel at room temperature, and while stirring, 5 parts of methanol and 0.4 parts of the copolymer shown in Table 1 were charged to obtain a composition. This composition was completely uniformly dispersed. The composition was left at room temperature and 5° C. for 60 days, and its transmittance was measured.

The results are shown in Table 1.

However, the transmittance was measured at 20° C. at a wavelength of 450 mμ using a cell with a thickness of 2 mm. The lower the transmittance, the more uniform the dispersion state.

Table 1 (The ω component ratio is on a molar basis.

Example 7 100 parts of light oil was charged into a stainless steel container at room temperature, and while stirring, 10 parts of methanol, 096 parts of water, 0.3 part of the copolymer of Example 2, and an average degree of saponification of 45 mol% and an average degree of polymerization of 40.
A composition was obtained by charging 0.08 parts of partially saponified polyvinyl acetate. Transmittance after leaving 308 at room temperature is 0.1%
, the transmittance after being left at 5°C for 30 days was 0. +%.

Example 8 2.0 parts of the polymer of Example 5, 100 parts of heavy oil, and 5 parts of methanol were mixed with stirring. This system was uniformly dispersed. No phase separation was observed even after standing at 5°C for 50 days.

Examples 9-10 Asphalt (Example?) was used instead of light oil in Example 2.
) and C heavy oil (Example 10) were used. The system was homogeneously dispersed. 60 at 5℃
No phase separation was observed even after standing for several days.

Example 12 100 parts of heavy oil C was charged into a stainless steel container at room temperature, and while stirring, 5 parts of methanol, 0.2 parts of water, and 0.7 parts of the copolymer of Example were added to obtain a composition. No phase separation was observed even after being left at 5°C for 60 days.

Claims (1)

[Scope of Claims] 1 selected from (a) water and/or alcohol, (b) solid hydrocarbons, and (c) liquid hydrocarbons;
A fuel composition comprising a hydrocarbon mixture comprising a combination of at least two of (b) and (c), and a vinyl copolymer having an oxyalkylene group. 2. A hydrocarbon-based mixture consisting of a combination of at least two of (a) water and/or alcohol, (middle) solid hydrocarbons, (c) liquid hydrocarbons), (b), and (c); A fuel composition containing a vinyl copolymer having an oxyalkylene group and a hydrophobic group in its side chain. 6 The vinyl copolymer is (c)) a vinyl monomer containing an oxyethylene group represented by the general formula +CH2,CH2O+i1H [where n is an integer from 1 to 100], CB) a t-class aliphatic saturated carbon Vinyl ester of acid and/or lower alkyl ester of ethylenically unsaturated carboxylic acid, C) (A) of vinyl monomer containing a hydrophobic group, ■)
, C), which is a multicomponent copolymer consisting of
Compositions as described in Section.