JPS59120689A - Gelled liquefied petroleum gas fuel - Google Patents

Abstract

PURPOSE:To provide a liquefied petroleum gas fuel in gel excellent in storage stability over a long period and in combustibility, prepared by mixing a polyacrylic acid (salt), liquefied petroleum gas and a solvent soluble in both of them. CONSTITUTION:A polyacrylic acid having an average molecular weight of 500,000-5,000,000 or salt thereof is added to a solvent which is soluble in both the polyacrylic acid (salt) and liquefied petroleum gas (e.g. ethanol or isopropanol) and, when necessary, the mixture is neutralized with an amine (e.g. laurylamine or stearylamine). the mixed solution is added to liquefied petroleum gas and, after stirring, the mixture is left standing for gelation to obtain the aimed liquefied petroleum gas fuel. The gelled fuel is stable over a long period and shows excellent combustibility. It has high-level safety, for there is no hazard of flowing-out, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a gel-like liquefied petroleum gas fuel with excellent stability, which is obtained by mixing liquefied petroleum gas fuel and a specific additive.

Liquefied petroleum gas fuels such as BK, butane, and propane are pressurized to several atmospheres to 1 o several atmospheres 8 E or -1 to -50 at room temperature.
Currently, it is cooled to below ℃ and filled into cylinders in a liquid state.

A major problem with cylinders filled with large amounts of liquefied petroleum gas fuel is how to properly prevent liquefied petroleum gas from spilling out when the cylinder overturns or breaks.

For example, in the case of household fuel, commercial fuel, etc., there are cases where liquefied petroleum gas spills due to a mistake when attaching or removing a cylinder to a fuel pipe, a liquefied petroleum gas spill due to cylinder overturning or damage due to an earthquake or fire, etc. In the case of automobile fuel, liquefied petroleum gas spills occur when cylinders rupture due to automobile accidents.

In addition, in the case of lighters, portable gas cylinders for tabletop stoves, and cylinders for hiking and mountaineering stoves, which have recently become widespread, if the cylinder were to break, liquefied petroleum gas could leak out, especially in rooms at home. narrow spaces such as inside a tent,
Also, spill accidents in cars, trains, etc. may be extremely dangerous.

Considering these points, it is considered that solid fuel having a sublimation or a vaporization form similar to sublimation is optimal as the fuel to be filled into the cylinder. However, liquefied petroleum gas assumes a solid state at around -120 to -180°C, making it practically impossible to use. Therefore, if it is possible to eliminate the fluidity of liquefied petroleum gas and directly mix /L through only gas in that state, then it is actually 1
3L ('This could be applied to the same purpose as sublimating solid/fuel 1.

As a result of intensive research, the inventor': Tsuyoshi discovered that the above-mentioned problems can be solved by converting liquefied petroleum gas fuel into a gel state. The fluidity of gelled liquefied petroleum gas 1 (σ is extremely small compared to liquid petroleum gas 4).
Because it is semi-solid, it can completely eliminate the problems encountered with conventional liquid fuels.

As mentioned above, creating gel-like liquefied petroleum gas.
2. Safety - 1 - Very important, and it has been considered urgent to search for an additive, a so-called gelling agent, that can create such a gel.

However, 7. Research and development on conventional gelling agents (d.
/ Komonokanitondo, such as butane, solo bread, etc.
At room temperature, the pressure is between several atmospheres and several atmospheres [l pressure, otherwise it will not be in a liquid state.
When cooled to 50°C, the so-called liquefied petroleum gas, which does not become liquid, remains stable for a long period of time (it remains in the form of a gel).

In view of the above circumstances, the inventor's tongue is stable for a long period of time,
In order to create a gel-like liquefied petroleum gas composition that is sufficiently durable for practical use and to develop a sulfur additive, the present invention was completed as a result of many years of intensive research. An object of the present invention is to provide a gel-like liquefied petroleum gas fuel with excellent storage stability and combustibility.

The above object of the present invention is to provide [A] polyacrylic acid or its salt having an average molecular weight M of 500,000 to 5,000,000, and [B] a solvent soluble in both polyacrylic acid or its salt and liquefied petroleum gas. , [C] A gel-like liquefied petroleum gas fuel obtained from liquefied petroleum gas/fuel.

The polyacrylic acid used in the present invention is a class-r compound having an N' average molecular weight of 500,000 to 5,000,000.

If the average molecular weight is less than 500,000, it will not exhibit an excellent thickening effect at low concentrations, making it impossible to obtain a stable gel-like liquefied petroleum gas fuel. In addition, if the average molecular weight exceeds 5 million, it can be uniformly dissolved in a small amount of solvent.
It becomes enlightenment.

The polyacrylic acid used in the present invention is an acidic substance,
It is easy to disperse it in an appropriate solvent (it has the property of forming a gel. Therefore, it is possible to make an acidic gel-like liquefied petroleum gas fuel, but in order to further enhance the gelling effect of polyacrylic acid) It is necessary to neutralize by adding a suitable alkaline neutralizing agent. As a neutralizing agent, long amines are suitable (7). For example, 2-ethylhexylamine, triamylamine, decylamine, laurylamine , myristylamine, stearylamine, etc. to a depth of 7J11 to neutralize.

Since the polyacrylate used in the present invention is water-soluble, even if 7J11 L is added to liquefied petroleum gas, only a white precipitate appears and no thickening occurs. It is important to add an appropriate amount of #lwi polar solvent to both. , polar solvents include lower alcohols such as methanol, ethanol, and infropanol.

ing.

Gel-like liquefied petroleum gas fuels are generally classified into lyophilic colloid-type gel fuels, oil-in-water droplet-type gel fuels, scaffold structure-type gel fuels, etc. based on their structural differences. It will be done.

Lyophilic colloid type gel fuel is a viscous solution obtained by adding 20 to 30% wax to liquefied fuel such as bromine or butane, and its pour point increases, so it can be heated at room temperature. It is completely gelled. No gelling agent is required to produce this type of fuel.

In addition, oil-in-water gel fuel is an emulsion in which a dispersed phase of liquefied fuel such as propane or furin is encapsulated one by one in water, which forms a continuous phase by a surfactant, and is kept stable. In addition, the frame structure type gel fuel has a three-dimensional framework made of surfactants such as fat and protein, and liquefied fuel such as propane and butane is incorporated into the framework, and the present invention The gel-like liquefied petroleum gas fuel belongs to this type. Because the membrane of this type of fuel 6 is made up of a two-dimensional three-dimensional skeleton and is strong, it becomes difficult to drain the liquid depending on the liquefaction state. Hateful.

In order to produce the frame structure type gelled liquefied petroleum gas of the present invention, polyacrylic acid is diluted with a polar solvent and a lower alcohol such as methanol, ethanol, isopropanol, etc., and left for about 1 hour. . A lower alcohol is further added to this mixture, and when the sweet polyacrylic acid is neutralized, a neutralizing agent amine is added. Further, this mixed solution and an additive are added to the liquefied petroleum gas in an amount of 1 or more and stirred for about 10 minutes. Immediately after production, it is a colloidal solution, but
After being exposed for about a day, it becomes a gel-like substance.

Here, when adding a neutralizing agent amine, the relationship between the amount of polyacrylic acid added and the neutralizing agent amine is as follows.
From 1/3 of Shun's acid equivalent to N sake amine is required.

In other words, if we use material 1 with 75 l-14 per acid as polyacrylic acid, 75? For polyacrylic acid,
The neutralizing agent amine is also required from 1/3 to 1 part [6]; for example, when laurylamine is used, 62 to 185 parts are required.

The amount of the monopolar solvent, i.e., the ibar-grade alcohol, needs to be added from twice to 10 times the amount of polyacrylic acid added.

Addition of polyacrylic acid 7J [I amount is liquefied petroleum gas fuel J
(1 to 5 parts by weight based on 00 weight) is preferable.

If it is less than 1 part by weight, it will be very difficult to produce gel-like liquefied petroleum gas, and even if it can be produced,
The stability of gel-like liquefied petroleum gas deteriorates, for example,
The drainage rate exceeds 5% after about 5 weeks after fabrication, and exceeds 10% after about 3 months. If the amount of polyacrylic acid added exceeds 5 parts by weight,
Although the stability of the gel-like liquefied petroleum gas after production is excellent, the combustibility may deteriorate, and there are also problems in terms of cost.

The liquefied petroleum gas fuel used in the present invention is a petroleum-based or natural gas-based hydrocarbon that is gaseous at normal temperature and pressure, such as propane, butane, and/or a mixture thereof, and is dispersed under pressure and/or cooling. means something that is.

In addition, in the present invention, freeze stabilizers such as ethylene glycol, zoropylene glycol, and diethylene glycol, various rust preventive agents, microbial generation inhibitors, and various cleaning agents may be used as necessary within a range that does not impair the stability of the gel. A gel-like liquefied petroleum gas fuel can be produced by using odorants, coloring agents, etc. alone or in combination.

Next, the present invention will be explained by examples, but the present invention is not limited to the following examples.

Example-1 Additives, abrasive solvents, and neutralizing agents listed in Table 1 (same as below for cooling only if necessary) and prescribed i+ of liquefied petroleum gas
Additives and neutralizing agents were added to an autoclave having a volume of 1000 cc using t, and a gel-like liquefied petroleum gas fuel was produced by the following production method.

1. First, polyacrylic acid is added to about 2/3 of the polar solvent to be added, and after stirring rapidly for 2 to 3 minutes, it is left to stand for about 1 hour. Further, about 1/3 of the remaining polar solvent and neutralizing agent are added to the liquefied petroleum gas and stirred for about 10 minutes.

Initially, this mixture was a light purple 710 ide solution, but 2
A transparent gel-like material having an apparent viscosity of about 50 to 200 voids was obtained when the mixture was left open for 4 hours.

Remaining 1 Example The gel-like liquefied petroleum gas fuel prepared in Example-1 was press-fitted into small cylinders of approximately 100 cc each to determine the storage stability of the gel and the combustion performance after 3 months. The test No. 1 was conducted.The results are as shown in the No. 2 test.

In both cases, it was confirmed that the product was stable for 1 hour, had good combustibility, and was practically usable. The ratio of the amount of liquid drained at ~ to the entire gel-like material is 0%, and the gel state is very good. Comparative Example-1 In Example-1, polyacrylic 1 is outside the average J'-
Gel-like 7H was prepared in the same manner as in Example-1 except that 30 swords, 2,450,000, 550, and 6,000,000 were used respectively.
I: Tried to obtain oil and gas fuel. However, when polyacrylic acid having an average molecular weight of 300,000 or 450,000 was used, the thickening effect was poor and a stable gel-like liquefied petroleum gas fuel could not be obtained. When polyacrylic acid having an average molecular weight of 5.5 million or 6 million was used, it did not dissolve uniformly in a small amount of solvent, causing problems in handling.

Patent applicant Mitsubishi Oil Corporation 71 Chugai Boeki Co., Ltd. Agent Patent attorney Nobuaki Sakaguchi (1 person) 689-

Claims (1)

[Scope of Claims] [A] Polyacrylic acid or its salt having an average molecular weight of 500,000 to 5,000,000, and [B] A solvent soluble in both polyacrylic acid or its salt and liquefied petroleum gas. and,〔
C] Gel-like liquefied petroleum gas fuel obtained from liquefied petroleum gas fuel.