JPH032400B2 - - Google Patents

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 heavy oil in order to improve its combustion efficiency and expand its use to light oil or medium oil, or it may be used to transport pulverized coal safely and efficiently. Practical applications such as dispersing fine powder in water, methanol, or hydrocarbon oil are expected. 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 saponified products thereof can be used as suitable safety agents. However, when this stabilizer is used, it has poor storage stability at low temperatures, so 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, and there is still room for further improvement. One thing became clear. However, the present inventors have discovered that a combination of at least two of (a), (b), and (c) selected from (a) water and/or alcohol, (b) solid hydrocarbons, and (c) liquid hydrocarbons. When a graft copolymer containing a polyoxyalkylene as a main component and a hydrophobic unsaturated compound as a branch component is blended into a hydrocarbon-based mixture, a novel fuel composition with excellent stability at low temperatures can be obtained. After discovering these effects, we have completed the present invention. As mentioned above, the stabilizer used in the present invention is obtained by graft copolymerizing a hydrophobic unsaturated compound onto the side chain of polyoxyalkylene, and the oxyalkylene component and the hydrophobic group component in the copolymer are copolymerized. The ability to uniformly disperse the hydrocarbons, alcohol, and water that work together to form the fuel composition provides performance that far exceeds that of conventional stabilizers. The graft copolymer is easily prepared by polymerizing a hydrophobic unsaturated compound in the presence of a polyoxyalkylene in a solvent or without the use of a solvent. Next, the chemicals used for producing the stabilizer used in the present invention will be explained. The polyoxyalkylene referred to in the present invention has the general formula

[Formula] [where R ¹ and R ² are hydrogen or an alkyl group, X is elemental, an organic residue such as an alkyl group, an alkyl ester group, an alkylamido group, a sulfonic acid group, and n is an integer from 5 to 100] It has the structure shown. 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. Practical polyoxyalkylenes in which the number n is advantageously 10 to 50, preferably 20 to 50, include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyethylene-polyoxypropylene block copolymers, etc. are effective. The hydrophobic group in the hydrophobic group-containing unsaturated compound refers to an alkyl group having 3 or more carbon atoms, a substituted alkyl group, and an aryl group. Examples of compounds that can be used in the present invention are shown below, but the present invention is not limited thereto. Vinyl esters of carboxylic acids Vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl palmitate, vinyl stearate, etc. Alkyl vinyl ether propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, tetradecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, etc. Alkyl allyl ether Propyl allyl ether, butyl allyl ether, hexyl allyl ether, octyl allyl ether, decyl allyl ether, dodecyl allyl ether, tetradecyl allyl ether, hexadecyl allyl ether, octadecyl allyl ether, etc. Ethylenically unsaturated carboxylic acid alkyl ester propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, Decyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, others,
Malenic acid monoalkyl ester, maleic acid dialkyl ester, crotonic acid alkyl ester, itaconic acid alkyl ester, sorbic acid alkyl ester, oleic acid alkyl ester, etc. Allyl esters of saturated carboxylic acids: allyl stearate, allyl laurate, allyl coconut oil fatty acid, allyl octylate, allyl butyrate, etc. α-olefin Propylene, α-hexene, α-octene, α
Decene, α-dodecene, α-hexadecene, α-
Octadesen et al. Other materials such as styrene and alkylamine (meth)acrylates can also be used. These hydrophobic group-containing unsaturated compounds may be used alone or in combination of two or more. In addition to these components, although not essential components, ethylenically unsaturated carboxylic acids (or their salts or amides), ethylenically unsaturated carboxylic acid lower alkyl esters, carboxylic acid vinyl esters, lower carboxylic acid allyl esters, and lower alkyl esters. It is also possible to copolymerize a small amount of vinyl ether, lower olefin, etc. Examples of such compounds are shown below. (meth)acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, vinyl formate,
Vinyl acetate, methyl (meth)acrylate, (meth)
Ethyl acrylate, methyl maleate, ethyl maleate, methyl crotonate, ethyl crotonate, methyl itaconate, ethyl itaconate, methyl sorbate, ethyl sorbate, methyl vinyl ether, ethyl vinyl ether, methyl allyl ether, ethyl allyl ether, allyl acetate,
Ethylene, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene monomethacrylate. The composition ratio of the graft copolymer used in the present invention varies somewhat depending on the type and composition of the target hydrocarbon mixture, but the proportion of the branch components to the trunk component is 30 to 300.
A mole %, preferably 50 to 150 mole % is preferred. The amount of the graft copolymer used in the present invention varies depending on the type of target 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. It is. The polymer can be added in the form of powder, block, or solution. In the present invention, the average saponification degree is further 95 mol%.
Hereinafter, 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-mentioned polyvinyl acetate resins, partially saponified polyvinyl acetate with an average saponification degree of 90 mol% or less, particularly preferably 0 to 60 mol%, and an average polymerization degree of 50 to 1000, that is, low saponification degree and low polymerization Particularly effective are partially saponified products. 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. Furthermore, the polyvinyl acetate resin can be added in the form of powder, block, or solution. Examples of solutions include aqueous solution, methanol solution, ethanol solution, 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 varies somewhat depending on the type of the mixed liquid 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 total composition. The effect is particularly remarkable when the polyvinyl acetate resin is used in an amount of 5 to 90% by weight based on the copolymer. In the present invention, methanol is typically used as the alcohol, but higher alcohols such as ethanol, propanol, and butanol can also be used. Examples of solid hydrocarbons include coal, asphalt, coal tar, pitch, and the like. Furthermore, liquid hydrocarbons include gasoline (for automobiles and aviation);
Jet fuel oil, kerosene, light oil, 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 with a boiling point of 200° C. or higher. The hydrocarbon mixture targeted by the present invention is selected from (a), (b), and (c) selected from (a) water and/or alcohol, (b) solid hydrocarbons, and (c) liquid hydrocarbons. Any combination of two or more of them may be used. From a practical standpoint, the preferred combination is gasoline/
Methanol, light oil/methanol, heavy oil/methanol, coal/methanol, coal/ethanol, asphalt/methanol, coal/water, asphalt/water, etc., but especially light oil/methanol, heavy oil/methanol, or asphalt/methanol. The effect is noticeable. The mixing ratio in the mixture is not particularly limited and may be selected from any range depending on the purpose. For example, when mixing methanol with heavy oil, 30% by weight or less of methanol is practically used. When preparing the composition of the present invention, there are no restrictions on the mixing means, as long as water, alcohol, solid hydrocarbon, liquid hydrocarbon, and copolymer or polyvinyl acetate resin are mixed with stirring. good. 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 explained in more detail by giving examples. Parts or percentages are by weight unless otherwise specified. Examples 1 to 6 100 parts of diesel oil was charged into a stainless steel container at room temperature, and while stirring, 5 parts of methanol and the copolymer shown in Table 1 were added.
A composition was obtained by charging 0.4 parts. The composition was completely uniformly dispersed. The composition was left at room temperature and 5° C. for 30 days, and its transmittance was measured. The results are shown in Table 1. However, the transmittance is 430 mμ using a 2 mm thick cell.
Measurements were made at 20°C at a wavelength of The lower the transmittance, the more uniform the dispersion state.

[Table] Example 9 100 parts of diesel oil was charged into a stainless steel container at room temperature, and while stirring, 10 parts of methanol, 0.3 parts of water, 0.3 parts of the graft copolymer of Example 1, and an average saponification degree of 45 mol%, an average polymer A composition was obtained by charging 0.08 part of partially saponified polyvinyl acetate of 400. The transmittance after being left at room temperature for 30 days was 5%, and the transmittance after being left at 5°C for 30 days was 7%. Example 10 2.0 parts of the graft copolymer of Example 5 and 100 parts of A heavy oil
1 part and 5 parts of methanol were mixed with stirring. This system was in a uniformly dispersed state. No phase separation was observed even after being left at 5°C for 30 days. Examples 11-12 The same experiment as in Example 9 was conducted except that asphalt (Example 11) and C heavy oil (Example 12) were used instead of light oil in Example 9. The system was uniformly dispersed. No phase separation was observed even after being left at 5°C for 30 days. Example 13 100 parts of C heavy oil was charged into a stainless steel container at room temperature, and while stirring, 5 parts of methanol and 0.2 parts of water were added, Example 2
A composition was obtained by adding 0.7 part of the graftomer. 5
No phase separation was observed even after being left at ℃ for 30 days.

Claims (1)

[Claims] 1. A hydrocarbon mixture consisting of a combination of at least two of (a), (b), and (c) selected from (a) water and/or alcohol, (b) solid hydrocarbons, and (c) liquid hydrocarbons. and a graft copolymer having a polyoxyalkylene as a main component and a hydrophobic unsaturated compound as a branch component.