JPS6033877B2 - Additive for pulverized coal-oil mixture - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an agent for improving the stability of a dispersion-based mixture of pulverized coal and oil obtained by a dry grinding process.

Conventionally, although pulverized coal has a low price per calorific value, it has the disadvantages of being difficult to transport, difficult to control during combustion, low calorific value, and requiring a large amount of space for storage. However, there was a problem with the fuel.

A mixture of pulverized coal and oil does not have the above-mentioned drawbacks and has high practical value because it has a lower price per calorific value than oil alone.
However, simply mixing pulverized coal and oil does not yield a satisfactory pulverized coal-oil mixture because the pulverized coal particles settle and separate due to the difference in specific gravity, coagulate, and lose fluidity. Therefore, it is important to find and introduce additives that improve stability.For example, in 1913, Mr. Brozon of Russia,
Mr. Greenstreet of England in 1920, Mr. Leadbeater in 1922, Mr. Balcke in Germany in 1932, and Mr. Uhde of Germany in 193, were examined.

However, soap, milk, gelatin, starch, albumin,
Rubber, heavy paraffin, cyclic olefin, resinate,
Additives such as oleate, stearate, palmitate, creosote oil, alkali, anthracene oil, tar, phenol, pyridine, aniline, naphthalene, etc. may not be added to the produced fine coal even if they are used together in an amount of 1% by weight or more. - The stability of the oil mixture is poor (less than one month) and the amount of additives is large, making the price of the pulverized coal-oil mixture high;
It was not put into practical use due to problems with stability and economy. An example of this can also be seen in U.S. Patent No. 3,615,095.
There were problems in practical use because of poor stability and the large amount of additives required.

In order to overcome the above-mentioned problems and put into practical use a finely divided coal-oil mixture using the dispersion method, the present inventors have conducted extensive research and have found that the effectiveness of the mixture of finely divided coal and oil obtained by the dry crushing method has been found to be effective. They succeeded in finding a suitable additive and made it possible to put it into practical use.

The present invention improves stability by more than three times compared to conventional methods, and even when stored for a long period of time at room temperature or high temperature, sedimentation of fine coal hardly occurs, and even if it occurs slightly, due to the excellent action of this drug, Because there is almost no agglomeration of settled pulverulent coal,
It can be re-liquidized with just a simple Takaazusa.

Of course, if it is for a short period of time (about 15 days), there is no need to cross the ocean. This has made it possible to transport the pulverized coal-oil mixture in tankers over long periods of time and to transport it through pipelines and piping. In addition, this drug requires less use than conventional methods, and from an economical point of view, it is better to use powdered coal.
We were able to further promote the practical application of oil mixtures. The coals used in the pulverized coal-oil mixture include various types of coal, such as anthracite, blue coal, submerged coal, lignite, etc., regardless of type or production area, and regardless of chemical composition or moisture content. Anything can be used. If such coal is dry-pulverized using an ordinary mill, powdered coal can be produced in large quantities. Moreover, there is no problem whether the moisture in the coal is removed by drying or not. However, lignite and other coals that contain a lot of water have a low calorific value per weight, so they are usually dried. Judging from the fuel property, the particle size of the powdered coal is usually preferably 20 French or less, and even smaller particle size of 10 French or less is preferable.
As far as physical properties such as stability of the pulverized coal-oil mixture are concerned, there is no problem even if the particle size is even larger.

The content of this pulverized coal is less than 60% by weight of the final mixture, and if it contains 6% or more by weight of pulverized coal,
This is not preferable because the viscosity becomes significantly high and fluidity is lost. If the amount is less than 2% by weight, it is also not preferred because there is little advantage in terms of price due to the inclusion of pulverized coal.

Therefore, less than 60% by weight can be mixed, but 20-50%
% by weight is more preferred.

In addition, the oil used in the pulverized coal-oil mixture includes coal crude oil, various fractions obtained from crude oil, such as kerosene, light oil, A heavy oil,
Mainly B heavy oil, C heavy oil, etc., this pond ethylene decomposition residual oil,
Oils and waste oils commonly used as fuel such as creosote oil, anthracene oil, and various blended oils, such as gas station waste oil (automobile lubricating oil, cleaning oil), ironworks waste oil (mixed oil of machine oil, cutting oil, cleaning oil, etc.) , waste oil from oil tankers and other ships, waste oil from general chemical factories, etc., and also includes mixtures of these.

Among these, it is particularly preferable to use petroleum crude oil, B heavy oil, and C heavy oil.

Even if you make a mixture using pre-blended oil,
A powdered coal-oil mixture may be prepared using a single oil (preferably petroleum crude oil or heavy oil) and then mixed or mixed with other oils.
Water may be mixed into the coal-oil mixture or added by the manufacturer, but transportation costs, storage costs, and other general and administrative costs increase by the volume of water. ,
Furthermore, it is not preferable because it increases the heat of evaporation and increases heat loss, so the smaller the amount, the better.

On the other hand, water has the property of improving the stability of the pulverized coal-oil mixture and has the effect of reducing the amount of NO and bysine in the exhaust gas during combustion.

Therefore, it can be used as desired depending on the purpose, but adding more than 50% by weight should be avoided as it inhibits combustion.

The additive for pulverized coal-oil mixtures produced by a dispersion method using a dry pulverization method according to the present invention is obtained by adding an alkylene oxide to a starting material having three or more active hydrogen atoms, and has an ethylene oxide group and a propylene group in the molecule. It contains at least an oxide group, has an ethylene oxide content of 3 to 8% by weight, preferably 10 to 4% by weight, and has a molecular weight of 1,000 to 100,000, preferably 7,000 to 10%. This additive contains a polyether compound as an essential component.

The additive for a mixture of pulverized coal and oil obtained by the dry pulverization method of the present invention can provide a stable pulverized coal-oil mixture by simply adding and mixing a very small amount of 1% by weight or less.

It goes without saying that the effect will not deteriorate even if it is added in an amount of 1% by weight or more, but the effect is significant even if it is added at 0.2% by weight, for example, and there is no need to add more for economic reasons.

In addition, this essential component may be used in combination with anionic, cationic, nonionic, or amphoteric surfactants, but as long as they do not exist in an amount of 5% or more, preferably 20% or more of the total amount of additives. No.

By the way, finely pulverizing coal using the Zeni-style pulverizing method
Since it has already been produced in large quantities, it can be said that this is the most preferable pulverization method for producing fuel that is regularly consumed in large quantities. When used in a pulverized coal-oil mixture containing at least less than % by weight of fuel oil, the new fuel can be supplied in large quantities because it exhibits the outstanding effects as described above.

Although the mechanism by which the agents of the present invention can exhibit outstanding effects when added in small amounts is not clear, it is likely that these agents adsorb to the surface of powdered coal particles in the oil, fully absorbing the repulsion and ion repulsion effects caused by the molecular chains of the agents. It is believed that this prevents the agglomeration and sedimentation of powdered coal particles.

From this point of view, in order to achieve the above effect with a small amount of addition, it is necessary to introduce a polar group for adsorption of drug molecules to the surface of powdered coal particles, and to physically prevent coal particle aggregation. It is thought that the size and bulk of the resulting molecules are required.

All the drugs of the present invention have such a molecular structure, have an ether bond based on a particularly polar ethylene oxide group in the molecule, and have a molecular weight of 1,000
It is characterized by a large value of 100,000 to 100,000, preferably 7,000 to 100,000.

As described above, all of the drugs of the present invention have polar groups, that is, hydrophilic groups, in their molecules, so when added to a powdered coal-oil mixture, they adsorb onto the surface of powdered coal particles, which have weak hydrophilic properties. Moreover, since the molecules are large and bulky, when the particles come close to each other, the steric hindrance of the molecules can prevent the particles from agglomerating and sedimentation, which is considered to be extremely effective.

The drug of the present invention is effective either after adding it to a mixture of oil and powdered coal obtained by a dry crushing method, or by adding powdered coal that has been added to oil in advance. .

If the pulverized coal-oil mixture to which the drug of the present invention has been added is subjected to a sieving process to uniformly dissolve or disperse the drug, a stable pulverized coal-oil mixture can be obtained.

Although the method is not particularly limited, if heating or strong heating is added at any point in the manufacturing process, the activity of the particle surface will increase and the adsorption of the drug will improve. - The performance of the oil mixture is further improved.
A strong cycle is usually 2 h/sec or more, preferably 1 h/sec or more, preferably 1 h/sec or more.
It refers to the addition of shear with a linear velocity of sec or more, and the shear can be of any type such as a propeller, turbine type, screen type, line mixer, homogenizer, colloid mill, etc., and this strong coagulation increases the activity of the surface of the powdered coal particles. rises,
The chance of contact between the drug and the particle surface is increased.

Further, the heating may be performed at a temperature of 50 qo or more, preferably 70 qo or more, and may be heated up to around 200 qo. The strength frame and heating may be applied at any time, for example, when coal is pulverized, when a chemical is added after pulverization, after the addition, during storage, or during pipe transportation. This drug is effective even without the addition of heat or strong rope, but when these conditions are added, the effect increases about twice as much.

Since the present pulverized coal-oil mixture utilizes the additive of the present invention, it can last for more than 5 months at room temperature and 90% even at 7000 °C.
It is very stable, with almost no difference in performance between the upper and lower layers for more than a day, and even when burned in a boiler or heating furnace, it can be burned in a manner similar to ordinary liquid fuel.

Furthermore, when water is included in the present mixture, it exhibits good effects such as improving flammability, reducing waste, and reducing N○×. Rust inhibitors, anti-pollution agents, as needed.
It is not a problem to use combustion improvers, water, carbon materials other than coal, etc. together. Specific examples of the additive for pulverized coal-oil mixtures of the present invention are shown below. The additive for pulverized coal-oil mixtures according to the present invention is obtained by adding alkylene oxide to a starting material having three or more active hydrogen atoms, and contains at least ethylene oxide and propylene oxide in the molecule, The content of ethylene oxide is 3 to 8% by weight, preferably 10 to 4% by weight, and the molecular weight is 1,
000 to 100,000, preferably 7,000 to 100,000 as an essential component.

The polyether mentioned here has the general formula Z [(RO)nH
] m , where Z is a starting material residue for the reaction having various functional groups.

Such starting materials include alcohols, amines, carboxylic acids or aromatic ring-containing compounds formalin condensates. To such a starting material, ethylene oxide (ethylene chlorohydrin or ethylene carbonate may also be used) and propylene oxide may be subjected to an addition reaction under pressure using a catalyst such as an alkali or an acid. Further, other alkylene oxides such as butylene oxide (including tetrahydrofuran) may be used in combination, if necessary. R
is an alkylene oxide residue, and n is the number of moles of alkylene oxide added. On the other hand, m is a number corresponding to the number of active hydrogens in the starting material, and is the number of alkylene oxide bonds to the active hydrogens. The number of moles of alkylene oxide added may be determined so that the molecular weight of the polyether compound is 1,000 to 10, preferably 7,000 to 100,000.
The content of ethylene oxide groups is from 3 to 8% by weight, preferably from 10 to 40%, based on the molecular weight of the final polyether compound.
The drug of the present invention can be easily obtained by reacting ethylene oxide, ethylene chlorohydrin, ethylene carbonate, etc. in such a manner as to obtain the desired amount by weight. Furthermore, the arrangement order of the ethylene oxide group and the propylene oxide group, and if necessary, other alkylene oxide groups, may be either a block copolymerization type or a random copolymerization type, but preferably a block copolymerization type is used as a part of the ethylene oxide group. Or it would be better if all of them were attached to the ends. A cylinder with a diameter of 5 mm and a height of 18 mm was filled with the pulverized coal-oil mixture shown in the Example Table (7,000 mm), and after standing for one month, the physical properties were measured and the effect of the additive of the present invention was evaluated.

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Claims (1)

[Claims] 1 Three or more active hydrogen atoms used to improve the stability of a pulverized coal-oil mixture produced by a dispersion method containing at least less than 60% by weight of pulverized coal obtained by a dry pulverization method and fuel oil. obtained by addition reaction of alkylene oxide to a starting material having An additive for a pulverized coal-oil mixture by a dispersion method, characterized in that it contains a polyether compound of 100,000 to 100,000.