JPS6027718B2 - Additive for pulverized coal-oil mixture - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the properties of a finely ground coal-oil mixture obtained by grinding coal in oil, preferably subjected to heating and a coagulation frame at some point in the production process. Relating to drugs that improve

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 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 their specific weight, coagulate, and lose fluidity. Therefore, it is important to discover and develop additives that improve the stability. This made it possible to put the mixture into practical use.

(JP-A-50202, JP-A-53-50203, JP-A-53-51209, JP-A-53-55305)
As a result of intensive research aimed at obtaining an oil mixture dispersion method, we found that by pulverizing coal in oil, adding heat and a strong sieve at some point in the manufacturing process, and adding a small amount of the agent according to the present invention. By doing so, we succeeded in obtaining a finely powdered coal-oil mixture using an excellent dispersion method.

The present invention improves the stability by more than twice that of the conventional method, and even when stored at room temperature or high temperature for a long period of time, there is almost no sedimentation of powdered coal, and even if it occurs a little, it is due to the excellent action of this drug. Since there is almost no agglomeration of settled pulverized coal, it can be re-fluidized with only simple grinding.

Of course, if it is for a short period of time (about 15 days), there is no need to use a rope. 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 pipes with peace of mind. In addition, the amount of this agent was less than that required in the past, and from an economical point of view, it was possible to further promote the practical use of pulverized coal-oil mixtures. The coal used in the pulverized coal-oil mixture includes various types of coal, such as anthracite, blue-green coal, head-roaring coal, lignite, etc., regardless of its type or production area, or regardless of its chemical composition or moisture content. , anything can be used.

The coal is put into oil either as it is or after it is crushed.
It is possible to make powdered coal directly in oil using various wet crushers. Moisture in coal may be removed before wet pulverization, during wet pulverization, or after pulverization, and there is no problem even if coal containing only a small amount of moisture is not removed.

Judging from the combustibility, the grain size of pulverized coal is usually preferably 200 microns or less, and even smaller particle size of 100 microns or less is preferred, but as far as the physical properties such as the stability of a single drop of pulverized coal are concerned, the particle size may be even smaller. There is no problem even if it is large. The content of this pulverized coal is 20% of the final mixture.
~7% by weight, and if it contains more than 70% fine coal, the viscosity will be extremely high and fluidity will be lost, which is undesirable, and if it is less than 20%, there will be little advantage in terms of price from containing fine coal. Unfavorable for a reason. Therefore, it is possible to mix 20 to 70%, but 30 to 60% is 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, B heavy oil, C heavy oil, etc.; oils and waste oils commonly used as fuel such as ethylene cracked oil, creosote oil, anthracene oil, various blended oils, etc.; Gas station waste oil (automobile lubricating oil, cleaning oil), ironworks waste oil (machine oil, cutting oil,
Mixed oil such as cleaning oil), waste oil from oil tankers and other ships, waste oil from general chemical factories, etc., and also includes mixtures of these oils.

Among these, it is particularly preferable to use petroleum crude oil, B heavy oil, or C heavy oil. 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 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 has the effect of reducing the amount of NO and bysine 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 mixture according to the present invention is an additive containing as an essential component at least one of the following drugs.

A sulfate ester of an aromatic sulfonic acid or alcohol having one sulfonic acid group or sulfate ester group in the molecule, or a salt of its counter ion.

Organic materials such as sulfuric acid, oleum, chlorosulfonic acid,
1. Sulfuric anhydride, acidic sodium sulfate, sulfamic acid, etc.
The drug according to the present invention can be obtained by reacting at a weight ratio such that one sulfonic acid group or sulfate ester group is bonded within the molecule. These can be broadly classified as follows: (1) Those in which the group is bonded to the core of a substance that has an aromatic ring.

Generally, a substance having an aromatic ring such as a benzene ring, a naphthalene ring, or an anthracene ring in its molecule can easily have one sulfonic acid group introduced therein by reacting with the above-mentioned sulfonating agent.

For example, sulfonated benzene, toluene, xylene, alkylbenzene, phenol, alkylphenol, styrene monomer, nahetalin, naphthol, alkylnaphthalene, aniline, nitroaniline, nitrobenzene, etc., which have one aromatic ring in the molecule, and Diphenyl, diphenyl ether, and derivatives thereof, each having two or more aromatic rings, are sulfonated. ■ Those in which the group is bonded to a substance that has a hydroxyl group or its precursor group.

Substances with hydroxyl groups, such as polyethylene glycol,
Polyhydric alcohols such as glycerin, bentaerythritol, polyalkylene glycols, alkylene glycol copolymers, aliphatic alcohols such as lower alcohols and higher alcohols, various alcohols, precursor groups of hydroxyl groups, such as 1011OX (X: halogen ) etc. can be easily subjected to sulfation reaction, and one such group can be introduced.

■ Mixtures The organic substances that can be sulfonated or sulfated can be mixed together, either by reacting a mixture of two or more to introduce the group, or by reacting each organic substance separately and introducing the group, and then mixing the two or more. good.

The above-mentioned drugs are merely representative examples, and the present invention is not limited thereto, nor is it intended to limit the manufacturing method for obtaining them.

No matter what method is used to obtain it, it is effective as long as it has one sulfonic acid group or sulfuric acid group in one molecule, and other groups may or may not be present.

In addition, although it would be ideal if strictly one such group was bonded within one molecule, even if the average bond value of the group is greater or smaller than 1, in the end there will be no bond within one molecule in the reactant. This is effective because it includes a substance having one such group. These agents may be present in the acid form (or in the form of counterions), such as metal salts such as sodium, potassium, calcium, magnesium, aluminum, iron, lead, nickel, ammonium salts, and alkylamines, alkanolamines, and aromatic amines. , pyridine and its derivatives, quaternized N-containing compounds, etc., and these salts may have an excess of either acid or base.

Further, the salt may be used after it is prepared, or the acid and the base to be paired may be used separately. At least one of the above
The additive for pulverized coal-oil mixtures of the present invention, which is characterized in that it contains at least 1% of pulverized coal, can provide a stable pulverized coal-oil mixture by adding only a very small amount of 1% by weight or less.

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 other anionic substances or nonionic substances, but it must be present in an amount of 5% or more, preferably 20% or more of the total amount of additives. The drug of the present invention is obtained by crushing coal in oil, preferably by heating and hardening at any point in the production process, and having an average particle size of 200 microns or less.
When used in a pulverized coal-oil mixture containing at least 7% by weight or less of total water content (3% by weight or less as added water content), the above-mentioned outstanding effects are exhibited.

The mechanism by which these chemicals can exhibit outstanding effects even when added in small amounts is that they adsorb to the surface of the powdered coal particles in the oil, fully exerting their entropic and ionic repulsion effects, and The purpose is to prevent sedimentation and agglomeration. The surface of coal particles is hydrophilic, and organic compounds with gutter properties are easily adsorbed. However, when coal is ground in oil, the surface of the powdered coal particles does not come into contact with air, compared to the surface of particles produced by dry grinding. Easy to stay active.

The drugs of the present invention, which have a sulfonic acid group or a sulfate ester group in common, are hydrophilic groups, and bind strongly to the surface of the powdered coal particles, which have strong hydrophilicity and activity, and even under various severe conditions. Demonstrate its outstanding effects.

Further, the reason why it is preferable to apply heating and strong tying at some point in the manufacturing process is to increase the activity of the particle surface and the adsorption of the drug.

Strong Azusa means usually 2m/sec or more, preferably low
It refers to adding a share of linear velocity of /sec or more,
The force may be in any form such as a propeller or a turbine, and this strong force increases the activity of the surface of the powdered coal particles and increases the chance of contact between the agent and the surface of the particles.

Further, the heating temperature is preferably 5000 qo or higher, preferably 70 qo or higher, and may be increased to around 200 qo. The heating and heating may be applied at any time, such as when the 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 the addition of heat or turmeric, the effect increases approximately twice as much when these conditions are added.

Since this mixture utilizes the additive of the present invention, it can be used for at least 3 months at room temperature, at least 70°C, and at 70°C.
For more than a month, there is almost no difference in performance between the upper and lower layers, and it is extremely stable, and even when burned in a boiler, it can be burned in a manner similar to ordinary liquid fuel.

The water in this mixture also improves flammability, reduces vizine,
This shows good effects such as a reduction in N0x. It is not a problem to use rust preventives, anti-pollution agents, refueling agents, etc. in combination as necessary. Typical examples using the additive for pulverized coal-oil mixtures of the present invention are described below.

(% is weight %) Notes on examples: "Pulverized coal kiln" is the weight-converted "resistance value" excluding volatile moisture, and the "resistance value" is the passing speed when a stainless steel rod (0 = 5, 20 g) is dropped vertically.

The larger the value, the softer it is. "Difference in coal concentration between the upper and lower layers" is expressed as the concentration in the lower layer minus the concentration in the upper layer.

The smaller the difference, the better. Examples (continued) Comparative examples

Claims (1)

[Claims] 1 Average particle size 200 obtained by crushing coal in oil
To improve the properties of a pulverized coal-oil mixture produced by a dispersion method, which contains at least 20 to 70% by weight of pulverized coal of less than μ and a total water content of 7% by weight or less (added water content of 3% by weight or less). A dispersion method characterized by containing at least one kind of an aromatic sulfonic acid having one sulfonic acid group or sulfuric ester group in the molecule, a sulfuric ester of an alcohol, or a counter ion salt thereof. Additive for pulverized coal-oil mixtures.