JPS6033873B2 - 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 result in 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 an important challenge to find additives that improve stability, for example, in 1913, Prozon of Russia, 1913.
Discussions were made by Mr. Greenstreet of England in 1922, Mr. Leadbeater of England in 1932, Mr. Balcke of Germany in 1932, and Mr. Uhde of Germany in 1932.

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 put into practical use a pulverized coal-oil mixture using a dispersion method, the present inventors have conducted extensive research and found that an effective additive to a pulverized coal-oil mixture obtained by a dry pulverization method has been found. succeeded in finding a drug,
This made practical application possible.

The present invention improves the stability by more than three times compared to the conventional method, and even when stored for a long period of time at room temperature or high temperature, 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. , because there is almost no agglomeration of settled pulverulent coal,
It can be re-liquidized with only a simple prayer.

Of course, in the case of a short period of time (about 15 days), there is no need to use a mixing pestle. This has made it possible to safely transport pulverized coal-oil mixtures over long periods of time in tankers, or to transport them through pipelines and piping. In addition, the amount of this drug 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 powdered coal-oil mixtures. The coal used in the fine coal-oil mixture includes, for example, anthracite coal, blue coal, subblue coal,
Any type of coal, such as lignite, can be used regardless of its type, origin, chemical composition, or moisture content. 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 properties, the particle size of the pulverized coal is usually preferably 200 French or less, and even smaller particle size of 100 French or less is preferred, but as far as the physical properties such as the stability of the pulverized coal-oil mixture are concerned,
Furthermore, there is no problem even if the particle size is large.

The content of this pulverized coal is less than 6% by weight of the final mixture, and if it contains more than 6% 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 6% by weight can be mixed, but 20-55%
% by weight is more preferred.

In addition, the oil used in the pulverized coal-oil mixture includes coal crude oil, various types of oil 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 fine coal-oil mixture using a single oil (preferably petroleum crude oil or heavy oil), other oils may be mixed or mixed.
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 N*x and vizine 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 additive for pulverized coal-oil mixture produced by a dispersion method using a dry pulverization method according to the present invention has a molecular weight of 1000 to
This additive contains as an essential component a compound obtained by crosslinking 100,000 polyether compounds with at least one selected from polyvalent isocyanate, polyvalent epoxy, and polyvalent aldehyde compounds.

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 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 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 physically prevent coal particles from agglomerating, in combination with the introduction of polar groups for adsorption of drug molecules to the surface of powdered coal particles. It is believed that molecular size and bulk are required.

All of the drugs of the present invention have such a molecular structure, and are characterized by the significant stericity and bulk of the molecular structure based on polar groups based on polyether groups and crosslinking of high molecular weight polyethers.

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. .

If the pulverized coal-oil mixture to which the drug of the present invention has been added is subjected to tampering and the drug is uniformly dissolved or dispersed, a stable pulverized coal-oil mixture can be obtained.

Although there are no particular limitations on the method, adding heat or strong heating at any point in the manufacturing process will increase the activity of the particle surface and improve drug adsorption. - The performance of the oil mixture is further improved.
A strong female pestle is usually 2 h/sec or more, preferably 1 blood/sec.
It refers to the application of shear with a linear velocity of sec or more, and the shear can be of any type, such as a propeller, turbine type, screw type, line mixer, homogenizer, colloid mill, etc., and this strong shear can increase 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 temperature may be increased to 5,000 degrees or more, preferably 70 degrees or more, and may be increased to around 200 degrees. The addition of strong base and heating may be done at any time, for example, when the coal is pulverized, when a chemical is added after pulverization, after the addition, during storage, or during pipe transportation. Although this drug is effective even without adding heat or strong massage, when these conditions are added, the effect increases about twice as much.

Because this pulverized coal-oil mixture utilizes the additive of the present invention, it can last for more than 5 months at room temperature, and can last up to 90% at 70qo.
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 pulverized coal-oil mixtures of the present invention are shown below.

The additive for pulverized coal overnight mixture according to the present invention has a molecular weight of 1
000 to 100,000, preferably 2,000 to 20,000 polyether compounds crosslinked with at least one selected from polyvalent isocyanate, polyvalent epoxy, and polyvalent aldehyde compounds.

The polyether compound referred to herein refers to a homopolymer or copolymer consisting of an alkylene oxide, such as ethylene oxide, propylene oxide, or butylene oxide, and at least one of ethylene chlorohydrin, ethylene carbonate, and tetrahydrofuran, and various active hydrogen groups. The molecular weight is arbitrarily selected from those obtained by polymerizing the above alkylene oxide and at least one of ethylene chlorohydrin, ethylene carbonate, and tetrahydrofuran to a starting material having at least 1, preferably 2 or more, to a predetermined molecular weight.

Here, when performing addition polymerization using two or more types of alkylene oxides, the addition mode may be random or flock. However, if the surfactant is a polymerization type, it is generally a block copolymerization type, and preferably, ethylene oxide is added to make the terminal end a hydrophilic group. Such polyether compounds can be effectively crosslinked either singly or in combination of two or more thereof, and of course, it is also possible to crosslink a single polyether compound and then blend two or more thereof. The active hydrogen groups mentioned here include alcoholic hydroxyl groups, amino groups, carboxylic acid groups,
Examples of starting materials containing one or more phenolic OH groups include the following.

Examples of alcohols include alcohols with one active hydrogen such as ethyl alcohol, butyl alcohol, and octyl alcohol; alcohols with two active hydrogens such as ethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, and polybutylene glycol. , butanediol, betanediol, hexanediol, etc., alcohols having 3 active hydrogen groups, such as glycerin, butanetriol, hexanetriol, trimethylolpropane, trietanolamin, etc., alcohols having 4 active hydrogen groups, e.g. Alcohols having 5 or more active hydrogen groups, such as diglycerin and bentaerythritol, such as sorbitan,
Sorbitol, glucose, sucrose, partially saponified polyvinyl acetate, partially saponified polyvinyl acetate copolymer, cell.

Starch, starch, etc. are useful, and even derivatives such as partially esterified alcohols having two or more active hydrogens can be used as long as one or more active hydrogens remain. In addition, examples of amines include amines having one active hydrogen such as dimethylamine and N-methyllaurylamine, amines having two active hydrogen such as methylamine, ethylamine, propylamine, butylamine, allylamine, etc. Amylamine, octylamine, dodecylamine, laurylamine, tetradecylamine, bentadecylamine, octadecylamine, tallow alkylamine, coconut alkyl amiso, aniline, p-
Toluidine, m-toluidine, nitroaniline, benzylamine, chloraniline, p-dodecylbenzylamine, cyclohexylamine, etc., amines having three active hydrogens, such as ammonia, beef tallow propylesodiamine, etc.
Amines having 4 active hydrogens, such as ethylenediamine, tetramethylenediamine, hexamethylenediamine,
Amines having 5 or more active hydrogens such as phenylenediamine, benzidine, cyclohexyldiamine, etc., such as diethylenetriamine, triethylenetetramine, tetraethylenebentamine, etc. are useful, and partial amides of amines having 2 or more active hydrogens, etc. Even various derivatives of can be used as long as one or more active hydrogen remains.

Examples of carboxylic acids include carboxylic acids having one active hydrogen, such as acetic acid, lauric acid, oleic acid, stearic acid, etc., and carboxylic acids having two active hydrogens, such as oxalic acid, malonic acid, phthalic acid, and fumaric acid. , maleic acid,
Glutaric acid, adipic acid, azelaic acid, sebacic acid,
Dodecanedioic acid, dimer acid, phthalic acid, isophthalic acid,
Carboxylic acids with 3 active hydrogens such as terephthalic acid and 0-phenylenediacetic acid; carboxylic acids with 4 active hydrogens such as hemimellitic acid, trimellitic acid, trimesic acid, etc., such as butanetetracarboxylic acid, pyromellitic acid, ethylenediaminetetracarboxylic acid, etc. Carboxylic acids having 5 or more active hydrogen atoms such as acetic acid, such as acrylic acid polymers, acrylic acid copolymers, maleic anhydride polymers, maleic anhydride copolymers, methacrylic acid polymers, methacrylic acid copolymers, acrylic Partially saponified products of polymers and copolymers of acids and methacrylic acid esters are useful, and various derivatives of these partially esterified products can also be used.

Examples of phenols include phenol, cresol, alkylphenol, resorcinol, cafcol, and hydroquinone, and other compounds having an aromatic OH group include naphthols.

These compounds having an aromatic OH group or their formalin condensates contain at least one phenolic O
Those having an H group are also useful. Furthermore, lactic acid, glycolic acid, N-substituted alkylglycine, glycine, malic acid, monoethanolamine, jetanolamine,
It does not matter if it contains different kinds of active hydrogens in the same molecule, such as tartaric acid and aminoethyl ethanolamine.

Examples of polyvalent isocyanate compounds include hexamethylene diisocyanate, tolylene diisocyanate, metaxylene diisocyanate, 1,5 naphthylene diisocyanate, 4,4 diphenylmethane diisocyanate, and polyvalent epoxy compounds include: These include diglycidyl bisphenol A, diglycidyl ethylene glycol, diglycidyl tetraoxyethylene glycol, and the like.

When a crosslinking agent is applied to these polyether compounds, the proportion of the crosslinking agent used is arbitrary, but generally it is 0.05 to 5 equivalents, preferably 0.1 to 5 equivalents, based on the terminal hydroxyl group equivalent of the polyether. Use 3 equivalents.

As for the crosslinking conditions, the polyether compound and the crosslinking agent are mixed, and the mixture is heated at 40 to 150 oO, preferably from 50 to 12
Heating is carried out in a range of 0.00000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000W]

A cylinder with a diameter of 5 cm and a height of 18 cm was filled with the pulverized coal-oil mixture shown in the example table, and after standing at 70 qo 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. Molecular weight 1000 to 100,000 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 pulverization method and fuel oil. A pulverized coal-oil mixture produced by a dispersion method, characterized in that it contains a compound obtained by crosslinking a polyether compound with at least one selected from a polyvalent isocyanate, a polyepoxy, and a polyvalent aldehyde compound. Additives for use.