JPS5823439B2 - Additive for pulverized coal-oil mixture - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an agent for improving the properties of pulverized coal-oil mixtures obtained by grinding coal in oil.

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 storage space. There was a problem with combustion.

A mixture of pulverized coal and oil does not have the above-mentioned drawbacks and has a lower price per calorific value than oil alone, so it has high practical value.

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, 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. I made it.

(Patent application 1977-125947, patent application 1977-12594
8. Patent application 1977-126406, patent application 1977-1302
39) The present inventors continued intensive research in order to obtain a pulverized coal-oil mixture that is stable for a longer period of time and is more economical, and as a result, an additive for a mixture obtained by pulverizing coal in oil was developed. As a result, he discovered that polyether and polyether derivatives were superior, and discovered that this product had amazing performance compared to conventional products, but after further investigation, he discovered that polyether derivatives In particular, by using a small amount of the agent according to the present invention, we succeeded in obtaining an even better pulverized coal-oil mixture.

The stability of the present invention has been improved by more than 3 times compared to conventional methods, and even when stored at room temperature or high temperature for a long period of time, pulverized coal will hardly settle, and even if it does occur a little, it is 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 the pulverized coal-oil mixture over long periods of time in tankers, store it in tanks, and transport it through pipelines and piping.

Additionally, this drug requires less use than conventional methods.
From an economic standpoint, the practical application of pulverized coal-oil mixtures could be further promoted.

The coal used in the pulverized coal-oil mixture includes various types of coal such as anthracite, bituminous coal, non-bituminous coal, and lignite, and any coal can be used regardless of its type, production area, chemical composition, or moisture content. .

Such coal may be directly pulverized in the oil by using various wet pulverizers, either as it is or by coarsely crushing it and placing it in oil.

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

The particle size of pulverized coal is determined from combustibility, and is usually an average particle size of 2.
00μ or less is preferable, and even smaller particle size is 100μ.
It is preferable that the particle size is less than μ, but as far as the physical properties such as the stability of the pulverized coal-oil mixture are concerned, there is no problem even if the particle size is larger.

The content of this pulverized coal is 20-70% of the final mixture
(wt%, the same applies hereinafter), and if it contains 70% or more of pulverized coal, the viscosity will significantly increase and fluidity will be lost, which is undesirable.If it contains pulverized coal of less than 20%, there will be economical Unfavorable as it reduces the benefits.

Therefore, it can be contained in an amount of 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,
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), ironworks waste oil (machine oil, cutting oil,
Cleaning oil and mixed oils), waste oil from oil tankers and other ships, waste oil from general chemical factories, etc., and also includes mixtures of these oils.

Among them, it is preferable to use petroleum crude oil, B heavy oil, and C heavy oil.

A pulverized coal-oil mixture may be made using a pre-mixed oil, or a pulverized coal-oil mixture may be made using a single oil (preferably petroleum crude oil or heavy oil), and then other oils may be mixed or co-fired. .

Water may be mixed into the pulverized coal-oil mixture or added by the manufacturer or user, but transportation costs, storage costs, and other general and administrative costs will be reduced by the volume of water. This is undesirable because it increases the heat of combustion and increases the heat loss due to the loss of heat of vaporization during combustion.The lower the value, the better.

- Power water has the property of improving the stability of the pulverized coal-oil mixture and has the effect of reducing NOx and byzine in the exhaust gas during combustion, so its inclusion in a small amount is allowed.

Therefore, the total water content is preferably 9% or less, preferably 6% or less, and there will be no problem if it does not contain any water at all.

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

The additive for pulverized coal-oil mixtures according to the present invention is at least one of the acids of sulfonated, sulfuric ester, or phosphoric esters of polyether compounds having a molecular weight of 3,000 to 100,000, or salts of counterions thereof. It is characterized by containing one or more kinds as essential components.

The polyether compound referred to herein is a compound represented by the general formula 2 (%)), where Z is a residue of a reaction starting material having various functional groups.

The starting material may be subjected to an addition reaction using at least one of various alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, etc., generally under pressure using a catalyst such as an alkali or acid.

Additionally, ethylene chlorohydrin and ethylene carbonate can also be used.

Further, R is an alkylene oxide residue, and n is the number of moles of alkylene oxide added.

On the other hand, m is a number corresponding to the active hydrogen group of the starting material, and is the number of alkylene oxide bonds to the active hydrogen group.

The alkylene oxide may be used alone or in combination of two or more types, and the arrangement order thereof may be independent and either a block copolymerization type or a random copolymerization type may be used.

That is, it contains at least one kind of various alkylene oxides and has a molecular weight of 1,000 to 100,000, preferably 3
000 to 100,000 polyether may be used.

As starting materials for such polyethers, various substances having active hydrogen are effective, such as alcohols having one active hydrogen, such as evaporative methyl alcohol, ethyl alcohol, isoflobil alcohol, octyl alcohol, and oleyl alcohol. etc., alcohols with 2 active hydrogens, such as evaporated ethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, polybutylene glycol, butanediol, bentanediol, hexanediol, etc., 3 active hydrogens alcohol,
For example, glycerin, butanetriol, hexane l-I
J-ol, trimethylolpropane, triethanolamine, alcohols with 4 active hydrogen groups, such as diglycene, pentaerythyl IJ-tol, alcohols with 5 or more active hydrogen groups, such as sorbitol, sorbitan, glucose, sucrose, polyvinyl acetate Partially saponified products, partially saponified polyvinyl acetate copolymers, cellulose, starch, etc. are useful, and even partially esterified products of alcohols having two or more active hydrogens and their derivatives have one or more active hydrogens. Any remaining active hydrogen can be used.

In addition, amines are also useful, such as amines with one active hydrogen,
Amines having two active hydrogens, such as dimethylamine, N-methyl-laurylamine, etc., such as methylamine,
Ethylamine, propylamine, butylamine, allylamine, amylamine, octylamine, dodecylamine, laurylamine, tetradecylamine, octadecylamine, tallow alkylamine, coconut alkylamine,
Aniline, p-toluidine, m-toluidine, nitroaniline, benzylamine, chloraniline, p-dodecylbenzylamine, cyclohexylamine, etc., amines with 3 active hydrogens, e.g. ammonia, tallow propylene diamine, etc., 4 active hydrogens amines having five or more active hydrogens, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc., can be used.

Even various derivatives such as partial amides of amines having two or more active hydrogens can be used as long as one or more active hydrogens remain.

Carboxylic acids are also useful, such as carboxylic acids with one active hydrogen such as acetic acid, lauric acid, oleic acid, stearic acid, carboxylic acids with two active hydrogens such as evaxalic acid, malonic acid, phthalic acid, maleic acid, etc. Carboxylic acids with 3 active hydrogens such as glutaric acid, adipic acid, azelaic acid, sehamic acid, dobucanic acid, timer acid, o-phenylene diacetic acid, etc. Carboxylic acids with 4 active hydrogens such as hemimellitic acid, trimellitic acid, etc. Acids, such as butanetetracarboxylic acid, pyromellitic acid, ethylenediaminetetraacetic acid, etc., carboxylic acids having 5 or more active hydrogen atoms, such as acrylic acid polymers, acrylic acid copolymers, methacrylic acid polymers, methacrylic acid copolymers, Maleic anhydride polymers, maleic anhydride copolymers, partially saponified products of polymers and copolymers of acrylic esters and methacrylic esters, and acid halides of the above acids can be used, and partially esterified products of the above acids. Various derivatives such as amide and amide are also useful.

Phenols are also useful, such as phenol, cresol, alkylphenol, resorcinol, hydroquinone, and other aromatic OH compounds such as naphthols.

Compounds having at least one phenolic OH group formed by formalin condensation using these compounds having a phenolic OH group alone or in combination with other aromatic compounds can also be used.

Furthermore, substances that contain different types of active hydrogen within the same molecule, such as lactic acid, glycolic acid, N-substituted alkylglycine, glycine, malic acid, monoethanolamine, jetanolamine, aminoethylethanolamine, tartaric acid, etc. It doesn't matter.

However, the above starting materials are just one example, and are not limited thereto.

These polyether compounds also include crosslinked polyethers in which one or more OH groups remain in the molecule, other than the above-mentioned polyether compounds.

That is, a polyether compound having two or more OH groups, a polyhydric (two or more active hydrogen) carboxylic acid explained above, a polyhydric acid dichloride, acelaic acid dichloride, oxalic acid dichloride, phthalic acid dichloride, etc. Those that are reacted with carboxylic acid halides to form intramolecular or intermolecular crosslinks, or those that have two or more O
Polyethers having an H group, polyvalent incyanates such as tolylene diisocyanate, metaxylene diisocyanate, hexamethylene diisocyanate, polyvalent epoxy compounds such as diglycidyl bisphenol A1 diglycidyl ethylene glycol, diglycidyl tetraoxyethylene glycol, Various crosslinked products may be used, such as those obtained by reacting with one or more polyvalent aldehydes such as glyoxal and thiodiacetaldehyde to achieve intramolecular or intermolecular crosslinking.

Polyether compounds with at least one OH group remaining in the molecule and having a molecular weight of 3,000 to 100,000 easily react with, for example, sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, acidic sodium sulfate, sulfamic acid, etc. However, a sulfonic acid group or a sulfuric acid ester group can be introduced into the molecule.

Changing all or part of the OH group to a sulfate ester group,
The drug according to the present invention can be obtained by introducing a sulfonic acid group into an aromatic ring or an aliphatic double bond.

Naturally, compounds having both a sulfonic acid group and a sulfuric acid ester group in one molecule are also effective.

Further, when the OH group of the polyether is reacted with, for example, phosphorus pentoxide, metaphosphoric acid, thiophosphate, etc. in any proportion, monoester, diester, or polyester can be produced, and the drug of the present invention can be obtained.

Such agents of the present invention are used either in the acid form or preferably as a counterion salt.

For example, metal salts and ammonium salts of sulfur, potassium, calcium, magnesium, aluminum, iron, lead, nickel, etc., salts of the above-mentioned amines, and amine salts of quaternized N-containing compounds are useful. The salt may contain an excess of either the acid or the base.

The additive for pulverized coal-oil mixtures of the present invention can provide a stable pulverized coal-oil mixture simply by adding and mixing a very small amount of 1% or less.

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

In addition, this essential component may be used in combination with anionic, cationic, nonionic, or amphoteric surfactants, 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 is produced by pulverized coal 20 to 7% having an average particle size of 200μ or less, which is obtained by pulverizing coal in oil and preferably subjecting it to heating and strong stirring at any point in the production process.
When used in a pulverized coal-oil mixture containing at least 0% and a total water content of 9% or less (added water content of 3% or less), the above-mentioned outstanding effects are exhibited.

The mechanism by which these chemicals can exhibit outstanding effects even when added in small amounts is not obvious, but these chemicals are adsorbed to the surface of powdered coal particles in the oil, fully exerting their entropic and ion repelling effects. The purpose is to prevent settling and agglomeration of powdered coal particles.

The surface of coal particles is hydrophilic and easily adsorbs polar organic compounds, but compared to particle surfaces produced by dry pulverization, when coal is pulverized in oil, the surface of pulverized coal particles does not come in contact with air, so it remains in an active state. and facilitates drug adsorption.

From the above 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 additive molecules to the surface of powdered coal particles. It is thought that the size and bulk of the resulting molecules are required.

This drug has a large molecular weight of 3,000 to 100,000, is bulky, and has a polar group based on a polyether group and a sulfonic acid group, a sulfate ester group, or a phosphate ester group, which have even greater polarity in the molecule. It is thought that because it contains one or more types, it has excellent entropy repulsion, adsorption, and ion repulsion, and produces outstanding effects.

In addition, if heating and strong stirring are applied at any point in the manufacturing process, the activity of the particle surface and the adsorption of the drug will increase, thereby further improving the performance of the pulverized coal-oil mixture.

Strong stirring is usually 2 m /sec or more, preferably 1 m /sec or more.
It refers to the addition of a shear with a linear velocity of 0 m/sec or more, and any type of stirring may be used, such as a propeller, turbine type, screw type, line mixer, homogenizer, colloid mill, etc. This strong stirring increases the activity of the surface of the powdered coal particles. and the chance of contact between the drug and the particle surface increases.

Further, heating is preferably carried out at a temperature of 50°C or higher, preferably 70°C or higher, and may be heated to around 200°C.

Strong stirring or heating may be applied at any time, for example, when coal is crushed in oil, when a chemical is added after crushing, after the addition, during storage, or during pipe transportation.

This drug is effective even without heating or strong stirring, but when these conditions are added, the effect increases about twice as much.

Since this pulverized coal-oil mixture utilizes the additive of the present invention, it is extremely stable, with a performance of more than 3 months at room temperature and more than 1 month at 70°C, with almost no difference in performance between the upper and lower layers. Therefore, even when burned in a boiler, heating furnace, etc., combustion similar to ordinary liquid fuel can be performed.

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

It is not prohibited to use rust preventive agents, anti-pollution agents, combustion improvers, water, etc. in combination as necessary.

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

Example

Claims (1)

[Claims] 1. A sulfonated polyether compound having a molecular weight of 3,000 to 100,000, 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; An additive for a pulverized coal-oil mixture, characterized in that it contains as an essential component at least one kind of acid of a sulfuric acid ester or a phosphoric acid ester, or a salt of a counter ion thereof.