JPS5823437B2 - Additive for pulverized coal-oil mixture - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to agents that improve the properties of pulverized coal-oil mixtures.

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. However, there were problems 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, it is important to find additives that improve stability, and the present inventors have already succeeded in overcoming the above problems and finding effective additives, making it possible to put pulverized coal-oil mixtures into practical use. (Japanese Patent Application No. 51-125947, Japanese Patent Application No. 51-125948, Japanese Patent Application No. 51-126406, Japanese Patent Application No. 51-130239).

The present inventors have conducted intensive research to obtain a pulverized coal-oil mixture that is stable for a longer period of time and is more economical.As a result, the present inventors have developed the following as an additive for a mixture obtained by pulverizing coal in oil.
By utilizing small amounts of the agents according to the invention, it has been possible to obtain excellent pulverized coal-oil mixtures.

The present invention improves stability by more than three times compared to conventional methods, and even when stored at room temperature or high temperature for a long period of time, pulverized coal hardly settles, and even if a little sedimentation occurs, due to the excellent action of this drug, Since there is almost no aggregation of the settled pulverized coal, it can be re-fluidized with only simple stirring.

Of course, stirring is not necessary for a short period of time (about 15 days).

This has made it possible to safely transport pulverized coal-oil mixtures over long periods in tankers, and to transport them through pipelines and piping.

In addition, the amount of this agent used was smaller than that of the conventional method, and from an economical point of view, it was possible to further promote the practical application of pulverized coal-oil mixtures.

The coal used in the pulverized coal-oil mixture includes various coals such as anthracite, bituminous coal, sub-bituminous coal, and lignite, and any type of coal can be used regardless of its type and origin, as well as its chemical composition and moisture content. .

The coal is put into oil either as it is or after being crushed,
It may be pulverized directly in oil using various wet pulverizers.

Moisture in coal may be removed before wet pulverization, during wet pulverization, or after pulverization, and there is no problem even if coal containing a small amount of moisture is not removed.

Judging from the combustibility, the particle size of pulverized coal is usually preferably 200μ or less, and even smaller particle size of 100μ or less is preferred, but as far as physical properties such as stability of the pulverized coal-oil mixture are concerned, even larger particle sizes are preferred. There is no problem even if it is expensive.

The content of this pulverized coal is 20 to 70% by weight based on the final mixture. If the pulverized coal is contained in an amount of 70% or more, the viscosity becomes extremely high and fluidity is lost, which is not preferable.
If it is less than 20%, it is not preferred because the cost advantage of containing pulverized coal is small.

Therefore, 20-70% can be mixed, but 30-60%
is even more preferable.

In addition, the oil used in the pulverized coal-oil mixture includes petroleum crude oil, various fractions obtained from crude oil, such as kerosene, light oil, A heavy oil,
Oils and waste oils commonly used as fuel such as B heavy oil, C heavy oil, ethylene decomposition residual oil, creosote oil, anthracene oil, various blended oils, etc., such as gas station waste oil (automobile lubricating oil, cleaning oil), iron works waste oil ( Mixed oil (machine oil, cutting oil, cleaning oil, etc.), waste oil from oil tankers and other ships,
Refers to general chemical factory waste oil, etc., and also includes mutual mixtures thereof.

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

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 steals the heat of evaporation and increases heat loss, so the smaller the amount, the better.

On the other hand, since water has the property of improving the stability of the pulverized coal-oil mixture and the effect of reducing NO and byzine in the exhaust gas during combustion, a small amount of water is allowed.

Therefore, the total water content is preferably 7% by weight or less, and there is no problem even if it is not contained at all.

Since it is not necessary to actively add water, the amount of water added should normally be 3% by weight or less.

The additive for pulverized coal-oil mixtures according to the present invention is made from one or more of alcohols, amines, carboxylic acids, and derivatives thereof having at least 3 or more, preferably 5 or more active hydrogens in the molecule. As an essential component, polyether is added with alkylene oxide and has a molecular weight of 3,000 to 100,000, preferably 7,000 to 100,000.

The polyether mentioned here can be represented by the general formula %, where Z is a residue of an alcohol, amine, carboxylic acid, or a derivative thereof having at least 3 or more, preferably 5 or more active hydrogen atoms in the molecule. It is.

R is an alkylene oxide residue, such as an ethylene, propylene, butylene group, and n is a value determined by the degree of polymerization of the alkylene oxide.

m is the number of active hydrogens that Z has, and is at least 3 or more, preferably 5 or more.

RO may be used alone or in two or more types, and the arrangement order thereof may be a block copolymerization type or a random copolymerization type.

In the case of copolymer type surfactants,
It is generally a block copolymer type, and preferably ethylene oxide is added to make the end a hydrophilic group.

At least 3 or more active hydrogen atoms in the molecule represented by Z,
In alcohols, amines, carboxylic acids, and derivatives thereof having preferably 5 or more atoms, A/L/L-ols are active hydrogen atoms such as glycerin, butane l-IJol, hexanetriol, trimethylolpropane, triethanolamine, etc. Alcohols with 4 active hydrogen atoms, diglycerin, alcohols with 4 active hydrogen atoms such as pentaerythritol, sorbitan, sorbitol, glucose,
Alcohols having 5 or more active hydrogens such as sucrose, partially saponified polyvinyl acetate, partially saponified polyvinyl acetate copolymer, cellulose, starch are useful, and alcohols having 4 or more active hydrogens are useful. Even various derivatives such as partially esterified products of can be used as long as three or more active hydrogen atoms remain.

In addition, amines include amines having 3 active hydrogens, such as ammonia and tallow propylene diamine, and amines having 4 active hydrogens, such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, phenylenediamine, benzidine, and cyclohexyl. Amines having 5 or more active hydrogens such as diamines, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc., are useful, and even various derivatives such as partial amides of amines having 4 or more active hydrogens, It can be used if three or more active hydrogens remain.

In addition, carboxylic acid refers to carboxylic acids having three active hydrogen atoms, such as hemimellitic acid, trimellidic acid, and trimesic acid, and carboxylic acids having four active hydrogen atoms, such as butanetetracarboxylic acid, pyromellitic acid, and ethylenediaminetetraacetic acid. Carboxylic acids having 5 or more hydrogen atoms, such as acrylic acid polymers, acrylic acid copolymers, maleic anhydride polymers, maleic anhydride copolymers, methacrylic acid polymers,
Partially saponified products of methacrylic acid copolymers, polymers and copolymers of acrylic acid and methacrylic acid esters are useful, and various derivatives such as partially esterified products thereof can also be used.

Furthermore, Z may contain different types of functional groups within the same molecule.

For example, glycine, malic acid, monoethanolamine,
These include jetanolamine, tartaric acid, and aminoethylethanolamine.

It should be noted that the above-mentioned examples of components are merely representative examples, and it is clear that analogs may be used as long as they do not go beyond the gist of the present invention.

The additive for pulverized coal-oil mixtures of the present invention, which is characterized by containing at least one substance represented by the above formula 0, is a pulverized coal-oil mixture that is stable even when added in a very small amount of 1% by weight or less.
An oil mixture can be obtained.

The upper limit was set to 1% by weight for economic reasons; for example, even if the content is 0.5% by weight or less, excellent effects can be achieved.

Further, this essential component may be used in combination with an anionic, cationic, nonionic, or amphoteric surfactant, but it must be present in an amount of 5% or more, preferably 20% or more of the total amount of additives.

The agent of the present invention exhibits the above-mentioned outstanding effects when used in a pulverized coal-oil mixture containing at least 20 to 70% by weight of pulverized coal obtained by pulverizing coal in oil.

The mechanism by which these drugs can exhibit outstanding effects even when added in small amounts is that the chemical structure of these drugs has three or more,
Since alkylene oxide is attached to the starting material preferably having 5 or more active hydrogen atoms, it is steric and has a large molecular weight of 1,000 to 100,000, preferably 7,000 to 100,000, making it very bulky. Because it has alkylene oxide polar groups, it adsorbs to the surface of powdered coal particles,
It is assumed that this is because it promotes entropic repulsion between particles and prevents settling and agglomeration of powdered coal particles.

In addition, the surface of coal particles is hydrophilic and easily adsorbs polar organic compounds, but compared to the surface of dry pulverized particles, when coal is pulverized in oil, the surface of the pulverized coal particles does not come into contact with air, so they are less active. Easy to maintain condition.

The drug of the present invention strongly binds to the surface of the pulverized coal particles, which have strong hydrophilicity and activity, and exhibits its outstanding effects even under various severe conditions.

However, if heating and strong stirring are applied at any point in the manufacturing process, the activity of the particle surface and drug adsorption will increase, further improving performance.

Strong stirring is usually 2 m/sec or more, preferably l Q
This refers to adding a shear with a linear velocity of m/sec or more, and stirring can be done by any type of propeller, turbine, etc. This strong stirring increases the activity of the powdered coal particle surface and increases the chance of contact between the chemical and the particle surface. rises.

In addition, the heating temperature is preferably 50°C, preferably 70°C or higher, and 2
The temperature may be raised to around 00°C.

Strong stirring or heating may be applied at any time, such as when coal is crushed in oil, when a chemical is added after crushing, during storage, or when transported through a pipe.

Although this drug is effective even without heating or strong stirring, the effect increases approximately twice when these conditions are added.

Since this mixture uses the additive of the present invention, it is very stable for more than 3 months at room temperature and for more than 1 month at 70°C, with almost no difference in performance between the upper and lower layers, and is very stable for boilers, etc. Even when burned, combustion similar to normal liquid fuel can be achieved.

Additionally, the water in the present mixture exhibits positive effects such as improved flammability, reduced byzine, and reduced NOx.

It is not a problem to use rust preventive agents, anti-pollution agents, combustion improvers, etc., if necessary.

Typical examples using the additive for pulverized coal-oil mixtures of the present invention are described below.

Example

Claims (1)

[Claims] 1. An alcohol or amine having at least three active hydrogen atoms in the molecule, which is used to improve the properties of a pulverized coal-oil mixture containing at least 20 to 70% by weight of pulverized coal obtained by pulverizing coal in oil. , carboxylic acids and their derivatives as a starting material, alkylene oxide is added thereto, and the molecular weight is increased from 3000 to 3000.
An additive for a pulverized coal-oil mixture, characterized in that it contains polyether as an essential component.