JPS6033876B2 - 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, if pulverized coal and oil are simply mixed, a satisfactory pulverized coal-oil mixture cannot be obtained 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 issue.For example, in 1913, Mr. Brozon of Russia,
Considerations were made by Mr. Greenstreet of England in 20th King, Mr. Leadbeater of England in 1922, Mr. Balcke of Germany in 1932, and Mr. Uhde of Germany in 1932nd.

However, soap, milk, gelatin, starch, albumin,
Rubber, heavy paraffin, cyclic olefin, resinate,
Even when the amount of oleate, stearate, palmitate, creosote oil, alkali, anthracene oil, tar, phenol, pyridine, aniline, naphthalene, etc. - 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 reliquidized with only a very simple loss.

Of course, if it is for a short period of time (about 15 days), there is no need for a shelf frame. 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, 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. Coal used in the fine coal-oil mixture includes, for example, anthracite coal, noise coal, subbituminous 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 mm or less, and a smaller particle size of 100 mm or less is preferred, but as far as physical properties such as 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 60% by weight based on 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 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,
A powdered coal-oil mixture may be prepared using a single oil (preferably petroleum crude oil or heavy oil) and then mixed with other oils or mixed with rice bran.
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 NOx and NOG 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 powdered coal-oil mixture produced by the dispersion method using the dry grinding method according to the present invention has a molecular weight of 1,000.
This additive contains as an essential component a compound obtained by crosslinking 100,000 to 20,000, preferably 2,000 to 20,000 polyether compounds in the presence of a peroxide (radical generating catalyst).

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 ordinary aniosotropic, 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 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 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 of the drugs of the present invention have such a molecular structure, and are characterized by the remarkable stericity and bulkiness of the molecular structure based on the crosslinking of a polar group based on a polyether group and a high molecular weight bolyether.

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 or rounded, 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 containing the drug of the present invention can be obtained by subjecting the pulverized coal-oil mixture to a grinding process to uniformly dissolve or disperse the drug.

Although the method is not particularly limited to the pulverized coal method, if heating or adding a strong sieve at some point in the production process increases the activity of the particle surface and improves drug adsorption, the pulverized coal - The performance of the oil mixture is further improved.
Strong female frame is usually more than shoes/sec, preferably 1 blood/s
The term refers to adding a shear with a linear velocity of ec or more.The female propeller may be of any type, such as a propeller, turbine type, screen type, line mixer, homogenizer, or colloid mill. The probability of contact between the drug and the particle surface increases.

Further, the temperature may be heated to 5000°C or higher, preferably 7000°C or higher, and the temperature may be raised to around 200°C. The heating or heating 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. This drug is effective even without the addition of heat or a strong female frame, but when these conditions are added, the effect increases approximately twice.

Because this pulverized coal-oil mixture utilizes the additives of the present invention, it can last for more than 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.

Additionally, water when included in the present mixture exhibits positive effects such as improved flammability, reduced bysine, and reduced NOx. 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 overnight mixture of the present invention are shown below.

Next, the additive for powdered coal-oil mixture according to the present invention is a polyether compound having a molecular weight of 1,000 to 100,000, preferably 2,000 to 20,000, and a peroxide (radical generating catalyst).
It is characterized by using a compound crosslinked in the presence of.

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 copolymer type, it is generally a block copolymer type, and preferably, ethylene oxide is added to make the terminal 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.

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. Alcohols with 3 active hydrogen groups such as butanediol, betanediol, hexanediol, etc. Alcohols with 4 active hydrogen groups such as glycerin, butanetriol, hexanetriol, trimethylolpropane, triethanolamine, etc. Alcohols having 5 or more active hydrogen groups, such as glycerin, bentaerythritol, etc., such as sorbitan,
Solvitol, glucose, sucrose, partially saponified polyvinyl acetate, partially quesolated polyvinyl acetate copolymer, cellulose, starch, etc. are useful;
Even derivatives such as partially esterified alcohols having one 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-methylamine, amines having two active hydrogen such as methylamine, ethylamine, probylamine, butylamine, allylamine, etc. amylamine, octylamine, dodecylamine, laurylamine, tetradecylamine, bentadecylamine, octadecylamine, tallow alkylamine, coconut alkylamine, aniline, p-toluidine,
Amines with 3 active hydrogens such as m-toluidine, nitroaniline, benzylamine, chloraniline, p-dodecylbenzylamiso, cyclohexylamine, etc., amines with 4 active hydrogens such as ammonia, tallow propylene diamine, etc.
Amines having five or more active hydrogens, such as diethylenetriamine, triethylenetetramine, tetraethylenebentamine, etc., are useful. , various derivatives such as partial amides of amines having two or more active hydrogens can also be used as long as one or more active hydrogens remain.

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, ethylenediamine Carboxylic acids having 5 or more active hydrogen atoms such as tetraacetic acid, such as acrylic acid polymers, acrylic acid copolymers, maleic anhydride polymers, maleic anhydride copolymers, methacrylic acid polymers, methacrylic acid copolymers, Partially saponified products of 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, examples of phenols include phenol, cresol, alkylphenol, resorcinol, 7-col, hydroquinone, etc., 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 types of active hydrogen in the same molecule, such as tartaric acid, aminoethyl ethanolamine, etc.

In addition, the peroxides (radical generating catalysts) mentioned here include hydrogen peroxide, penzoyl peroxide (penzoyl peroxide), jeetahsharifthyl/gu oxide, kyumene/gu oxide, and dicumyl peroxide. etc. can be used arbitrarily.

The proportion of peroxide (radical generating catalyst) used can be arbitrarily used in the range of 0.05% to 1% by weight, preferably 0.1% to 5% by weight, based on the polyether. For example, Jo
Urnal.

f Applied P. I's mer Science
Vol. 7 pp. 461-468 (1963), etc., and these known techniques can be directly applied to the crosslinking referred to in the present invention. Generally, a predetermined amount of peroxide is mixed with polyethers in the presence or absence of a solvent, and 50 to 250, preferably 70 to 180,
The target substance can be obtained by reacting within a range of 100% and distilling off the solvent if necessary. The pulverized coal-oil mixture shown in the Examples table was filled into a cylinder with a diameter of 5 arcs and a height of 18 cm, and after standing at 70 CO for one month, the physical properties were measured and the effects of the additive of the present invention were evaluated.

ship ship Faith false the law of nature V Thought R Mountain Total Geikaun skin Nada millet member of staff Salmon NS Homura lotus poorfutsu C S is also carp ■ cloud snow cloud boat Iron school] Bonito K'n ＊＊＊ ＊ ＊l * ' hmm ★ Mi child height ○ q ~one" to ★ under ^ child debt Day ○ mouth : Ku- ＞ The under Enter ) .

Li.

shaku○ A

Claims (1)

[Claims] 1 Used for improving 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, with a molecular weight of 1,000 or more. An additive for pulverized coal-oil mixtures using a dispersion method, characterized by containing a compound obtained by crosslinking a polyether compound of 100,000 in the presence of a peroxide (radical generating catalyst).