JPS6033872B2 - 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 disadvantages such as difficulty in transportation, difficulty in controlling combustion, low calorific value, and large space required for storage. There was a problem with 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, finding additives that improve stability is an important challenge.
Mr. Greenstreet of England (1922), Mr. Leadbeater (1932) of Germany, Mr. Balcke (1932) of Germany, and Mr. Uhde (193) of Germany conducted a study.

However, soap, milk, gelatin, starch, albumin,
Rubber, heavy paraffin, cyclic olefin, resinate,
Even when additives such as oleate, stearate, palmitate, creosote oil, alkali, anthracene oil, tar, phenol, pyridine, aniline, naphthalene, etc. 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 commercialize the pulverized coal-oil mixture obtained by the dispersion method, the present inventors have conducted extensive research and have found an effective solution for the pulverized coal-oil mixture obtained by the dry pulverization method. succeeded in finding an additive,
This made practical application possible.

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-fluidized with only a very simple flocculation.

Of course, if it is for a short period of time (about 15 days), there is no need to use a lily pad. This has made it possible to safely transport the pulverized coal-oil mixture in tankers over long periods of time, or to transport it through pipelines and piping. In addition, this agent requires less consumption than conventional agents, and is economically viable.
We were able to further promote the practical application of oil mixtures. The coal used in the pulverized coal-oil mixture includes various types of coal, such as anthracite, light blue coal, subblue 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. Further, there is no problem whether the moisture in the coal is removed by drying or not. However, lignite, etc., which have a high moisture content, have a small calorific value per weight, so they are usually dried. Judging from the fuel properties, the particle size of the fine coal is usually preferably 200 French or less, and even smaller particle size of 100 French or less is preferred, but as far as physical properties such as stability of the pulverized coal-oil mixture are concerned, the particle size may be even larger. There is no problem even if the size is large.

The content of this pulverized coal is less than 60% by weight based on the final mixture, and if pulverized coal with a weight of 6 or more is contained, the viscosity becomes extremely high and fluidity is lost, which is not preferable. 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 to 55% 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., as well as ethylene cracked 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 powdered coal-oil mixture using pre-mixed oil,
After making a pulverized coal-oil mixture using a single oil (preferably petroleum crude oil or heavy oil), other oils may be mixed or co-fired.
Water may be mixed into the pulverized coal-oil mixture or added by the manufacturer, but the volume of water increases transportation costs, storage costs, and other general and administrative costs. ,
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 N○× and byzine in the exhaust gas during combustion.

Therefore, it can be used as desired depending on the purpose, but adding more than 5% by weight should be avoided as it inhibits combustion.

The pulverized coal-oil mixture additive produced by the dispersion method using the dry grinding method according to the present invention has one or more phenolic OH groups, preferably two or more, and has two or more total active hydrogen groups. Preferably, the additive contains as an essential component a polyether having a molecular weight of 3,000 to 10,000, preferably 7,000 to 100,000 by adding an alkylene oxide to an organic compound having three or more as a starting material.

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. 1
It goes without saying that the effect will not deteriorate if more than 0.2% by weight is added, but the effect is significant even at about 0.2% by weight, and there is no need to add more for economical 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. It won't happen.

By the way, finely pulverizing coal using the dry pulverization 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 unclear, it is likely that these agents are adsorbed onto the surface of powdered coal particles in the oil, and the repulsion and ion repulsion effects caused by the molecular chains of the agents are more than sufficient. It is thought that it thins out and 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 agglomeration. 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 a polar group based on an ether bond of alkylene oxide, and have a molecular weight of 3,000 to 100,000, preferably 7,000.
It has a large size of 100,000 to 100,000, and because the starting material for the reaction has two or more active hydrogen atoms, preferably three or more, it is characterized by a 3-dimensional and bulky molecule.

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 to the surface of powdered coal particles, which have weak hydrophilicity, and Because the molecules are large and bulky, when the particles come close to each other, the steric hindrance of the molecules can prevent particle aggregation and sedimentation, which is thought 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. .

A stable pulverized coal-oil mixture to which the drug of the present invention has been added can be obtained by subjecting the mixture to a pulverized coal-oil mixture to uniformly dissolve or disperse the drug.

Although the female pestle method is not particularly limited, if heating or adding strong base sandalwood at any point in the manufacturing process increases the activity of the particle surface and improves drug adsorption, - The performance of the oil mixture is further improved.
Strong spot Azusa means usually 2h/sec or more, preferably 10m
It refers to adding a shear with a linear velocity of /sec or more,
The powder can be of any type, such as a propeller, turbine type, screw type, line mixer, homogenizer, colloid mill, etc. This strong powder increases the activity of the powdered coal particle surface and increases the chance of contact between the drug and the particle surface. do.

Further, the heating temperature may be increased to 5,000 degrees or higher, preferably 7,000 degrees or higher, and may be increased to around 200 degrees. The heat treatment may be applied at any time, for example, when the coal is crushed, when a chemical is added after the coal is crushed, after the coal has been crushed, during storage, or when transported through a pipe. Although this drug is effective even without the addition of heat or strong seaweed, when these conditions are added, the effect increases approximately twice as much.

Since this pulverized coal-oil mixture utilizes the additive of the present invention, it lasts for 5 months at room temperature and 90% at 70°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 vizine, and reducing N○x. It is not a problem to use rust preventives, anti-pollution agents, combustion improvers, water, carbon materials other than coal, etc., as necessary. Specific examples of the additive for the pulverized coal mixture of the present invention are shown below.

The additive for powdered coal-oil mixture according to the present invention has one or more phenolic OH groups in the molecule, preferably two or more,
And an organic compound having 2 or more, preferably 3 or more total active hydrogens is used as a starting material, and an alkylene oxide is reacted with the polyether to have a molecular weight of 3000 to 10, preferably 7000 to 10, as an essential component. It contains.

The polyether mentioned here is the general formula Z [(RO)nH]m where Z is the residue of the above starting material.

R is a residue of alkylene oxide such as ethylene, propylene, butylene, ethylene chlorohydrin, ethylene carbonate, or tetrahydrofuran, and n is a number determined by the degree of polymerization of the alkylene oxide. m is the number of active hydrogens including the phenolic OH group that Z has, and is at least 2 or more, preferably 3 or more. RO may be a single substance or two or more types thereof, and the arrangement order thereof may be a block copolymerization type or a random copolymerization type. However, if the surfactant is a copolymer type, it is generally a block copolymer type, and preferably, ethylene oxide is added to make the end a hydrophilic stem. Contains ethylene oxide and propylene oxide groups,
Those having an ethylene oxide group content of 3 to 80% by weight are suitable for the present invention.

Examples of starting materials corresponding to Z include:

(1) Polyhydric phenols such as catechol, resorcinol, hydroquinone, pyrogallol {2) Polyhydric naphthols such as dioxynaphthalene and trioxynaphthalene such as naphresorcin and Q-naphthohydroquinone {
Substituted phenols containing one or more, preferably two or more active hydrogens in addition to the 3' phenolic OH group, such as aminephenol, oxybenzoic acid, gallic acid4 Phenol, resorcinol, naphthol or substituted phenols, such as meth Cresol, meta-xylenol, metal ethylphenol, orthocresol, /gracresol,
2.6 A condensate containing at least two phenolic OH groups among the condensates of xylenol, etc., and aldehydes, such as formaldehyde, acetaldehyde, benzaldehyde, or ketones, such as acetone, under an acidic or basic catalyst. '5} Substituted phenols containing one or more, preferably two or more active hydrogens in addition to the phenolic OH group, such as aminophenol, oxybenzoic acid, gallic acid, etc., and aldehydes, such as formaldehyde, acetaldehyde, A condensate having at least two or more phenolic OH groups in the condensate condensed with benzaldehyde or ketones, for example acetone, under acidic or basic catalysts, where the phenolic O
H group means phenol, naphthol, substituted phenol,
It means an OH group directly bonded to the aromatic ring of substituted naphtholyl, polyhydric phenol, polyhydric naphthol, etc.

A cylinder with a diameter of 5 cm and a height of 18 arcs was filled with the pulverized coal-oil mixture shown in the Examples table (70 qo), and after being allowed to stand for one month, the physical properties were measured and the effects of the additive of the present invention were evaluated.

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Claims (1)

[Claims] 1. Phenolic OH groups used to improve the stability of a dispersion method pulverized coal-oil mixture containing at least less than 60% by weight of pulverized coal obtained by a dry grinding method and fuel oil. Using an organic compound having one or more and two or more total active hydrogens as a starting material,
Add alkylene oxide to increase the molecular weight from 3000 to 10
An additive for pulverized coal-oil mixtures using a dispersion method, characterized by containing a large amount of polyether.