JPS59115391A - Mixed fuel composition - Google Patents

Abstract

PURPOSE:To provide a mixed fuel composition which consists of powdered coal having a specified particle diameter distribution, a fuel oil and a stabilizer, with a high concentration of coal, low viscosity and excellent stability. CONSTITUTION:The composition is prepared by mixing 30-70wt% (dry weight) powdered coal, 15-70wt% fuel oil (e.g. heavy oil) and 0.1-5wt% surfactant (e.g. sodium di-2-ethylhexyl sulfosuccinate) and/or stabilizer consisting of a bituminous substance (e.g. coal tar pitch) in a propeller mixer, etc., followd by mixing in a high-speed mixer whch gives high shearing force. The powdered coal has such particle size distribution that particles of 1,500mu or smaller account for 100%, those of 300mu or smaller, 95-100%, those of 200mu or smaller, 80-90%, those of 100mu or smaller, 55-75%, those of 10mu or smaller, 15-35% and those of 1mu or smaller, 3-10% by cumulative weight percentage.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a mixed fuel composition, and more particularly to a mixed fuel composition consisting of coal powder having a specific particle size distribution, fuel oil, and a stabilizer, which has a high coal concentration, low viscosity, and is stable. The aim is to create a mixed fuel composition with good properties.

Due to oil price fluctuations and future supply concerns, coal-oil mixed fuel, or C
OM (Coal Oll Mixture) is beginning to be used. As described above, since COM is a mixed fuel intended to replace a portion of petroleum-based fuel with coal, it is clear that the higher the coal concentration in its composition, the more advantageous it is. However, the coal concentration in 00M currently being studied is 40-50i11, and if the coal concentration is higher than that, the viscosity becomes extremely high, which has the disadvantage of making handling such as transportation by a pump difficult. In addition, when attempting to increase the coal concentration by increasing the average particle size, there was a drawback that coal particles, which have a higher specific gravity than fuel oil, would settle and separate over time.

As a method for avoiding sedimentation and separation of coal particles, for example, in JP-A-53-117002, the particle size of coal is reduced to 10
It is pulverized until it becomes fine particles of less than μ in size, but in this case, not only does pulverization consume a large amount of power, but also the number of coal particles and the cumulative surface area of all particles increase significantly, so the viscosity of the obtained COM becomes extremely large. Become.

In order to improve these drawbacks, many surfactants (JP-A-53-47307, JP-A-53-4) have been used as stabilizers.
No. 7405, U.S. Patent No. 3,617,095, etc.) and bituminous substances (Japanese Patent No. 36881, JP-A-1560-1989, etc.)
No. 17, JP-A No. 57-153090, etc.), but none have yet shown sufficiently satisfactory effects.

The inventors of the present invention aimed to improve this shortcoming of COM (as a result of intensive research, they arrived at the present invention.

That is, the present invention provides a mixed fuel composition consisting of coal powder, fuel oil, and a stabilizer in which the cumulative weight percentage of coal powder particle size is 1500μ or less: 100%, 300P or less = 95
~ioo%, 200 μ or less: 80 to 90%, 100 μ or less: 55 to 75%, 10 μ or less: 15 to 35%, and 1 μ or less: 3 to 10 cm.

The feature of the present invention lies in the specific particle size distribution of the coal powder particles, and with such a distribution, even COM with a high coal concentration has a low viscosity and good stability.

This is considered to be due to the following reasons.

Particles over 300P are relatively coarse and therefore have a small contact area with fuel oil, so the coal concentration is high (but the viscosity is low). Fill in the gaps and finer 10 to 10
A particle of 0μ fills the next gap. Final gap is 1-10
/A fine particles and ultrafine particles of 1μ or less result in the closest packing of coal particles in fuel oil, but since the particle size distribution in the present invention is an ideal distribution, high concentration COM is obtained.

Furthermore, as stated in JP-A-53-117002, ultrafine particles of 1μ or less and fine particles of 10μ or less are stably dispersed in fuel oil, and the apparent specific gravity of a dispersion in which they are dispersed is that of coal particles. As a result, buoyancy is imparted to coarse coal particles.The dispersion in which buoyant coal particles are dispersed further imparts buoyancy to coarser particles.For this reason, it is stable. A COM with excellent performance can be obtained.

Coal used in the present invention includes anthracite, bituminous coal, sub-bituminous coal, and lignite, and fuel oil includes crude oil, gasoline, kerosene, light oil, heavy oil, and waste oils.

Stabilizers used in the present invention include surfactants or bituminous substances.

As the surfactant, known surfactants can be used, but
In particular, -503- group and/or 1050 group in the molecule
Anionic surfactants with 3-groups, quaternary ammonium salts and polyether compounds are preferred.

Typical examples of anionic surfactants having a -503- group and/or a 10503- group in the molecule include the following.

(11 Sulfonated aliphatic hydrocarbons Alkanesulfonic acids, olefinsulfonic acids, etc.

(2) Sulfonated aromatic compounds Petroleum sulfonic acid, lignin sulfonic acid, furkylbenzenesulfonic acid, naphthalene sulfonic acid, alkylnaphthalene sulfonic acid, alkylphenol sulfonic acid, formaldehyde condensates of these sulfonic acids, polystyrene sulfonic acid Such.

(3) α-sulfocarboxylic acid or its leather stel α
-Sulfo fatty acids, α-sulfo fatty acid alkyl esters,
Sulfosuccinic acid mono- or dialkyl esters, sulfosuccinic acid mono- or dialkenyl esters, etc.

(4) Alcohol sulfate ester Sulfuric esters of saturated or unsaturated alcohols.

(6) Sulfuric esters of polyoxyalkylene compounds, sulfuric esters of polyoxyalkylene alkyl or alkenyl ethers, sulfuric esters of polyoxyalkylene alkylphenyl ethers, sulfuric esters of polyoxyalkylene fatty acid esters, sulfuric esters of polyoxyalkylene aliphatic amines, Sulfuric esters of polyoxyalkylene fatty acid amide, sulfuric esters of polyoxyethylene polyoxybrobylene glycol, sulfuric esters of polyoxyethylene polyoxypropylene ethylene diamine, fullkylene oxide of polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, and sorbitol. Adducts such as sulfate esters.

(6) Sulfate esters of oils and fats Sulfated tall oil, sulfated animal and vegetable oils, etc.

Sono et al., amine salts, ammonium salts,
Metal salts are also used.

Amines that form salts include aliphatic amines and aromatic amines, such as methylamine, butylamine, laurylamine, stearylamine, oleylamine, dimethylamine, monoethanolamine, triethanolamine, morpholine, ethylenediamine, diethylenetriamine, and triamine. Examples include ethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine, and aniline.

Metals that form salts include potassium, sodium, lithium, barium, calcium, magnesium, aluminum, zinc, and iron.

Quaternary ammonium salts are known cationic surfactants having a quaternary ammonium group, and representative examples include compounds represented by the following general formula il+, as well as compounds having 6 to 22 carbon atoms.
There are alkylpyridinium halides, alkenylpyridinium halides, alkylpyridium halides, alkenylquinolinium halides, etc. that have a hydrocarbon group.

Here, Rx, R2, R3, R4 and R5 have 1 to 1 carbon atoms.
22 saturated or unsaturated chain hydrocarbon groups, hydroxyethyl group, hydroxypropyl group, benzyl group, or a substituent represented by formula (2), with a small number of carbon atoms (each has 6 to 22 carbon atoms).

RX(RlO)k(CH2+t...(2)(2)
In the formula, R+in, a saturated or unsaturated chain hydrocarbon group or acyl group having 1 to 22 carbon atoms, or a phenyl group substituted with a saturated or unsaturated chain hydrocarbon group having 1 to 18 carbon atoms, X is O or NR'(R' is H or a saturated or unsaturated hydrocarbon group having 1 to 22 carbon atoms),
Ro is a straight chain or side chain alkylene group having 1 to 4 carbon atoms, k
is 0-10olt is 1-3.

R6 in general formula (1) is a saturated or unsaturated chain hydrocarbon group having 1 to 3 carbon atoms, a hydroxyethyl group, a hydroxypropyl group, or a benzyl group, m is 1 to 3, and n is 1 to 1
00, X○ is chlorine ion, bromide ion, iodine ion,
These are 7 ions such as nitrate ion, sulfate ion, methyl sulfate ion, ethyl sulfate ion, perchlorine ion, paratoluenesulfonate ion, and fatty acid ion having 1 to 22 carbon atoms.

The polyether compound is a compound having a polyoxyalkylene group in the molecule, and has a molecular weight of 1,000 to 100,000, preferably 2,000 to 50,000.

The polyether compound used in the present invention is a compound having monovalent or polyvalent active hydrogen, that is, a compound having a hydroxyl group, a thiol group, an amino group, an imino group, a carboxyl group, etc., and a compound having ethylene oxide, propylene oxide, butylene oxide, It is a compound obtained by addition reaction of alkylene oxide such as tetrahydrofuran, and when two or more types of fullylene oxide are added, the addition form may be a random type or a random type.

Further, compounds obtained by crosslinking these compounds with polyvalent incyanate, polyvalent epoxide, polyvalent carboxylic acid, polyvalent carboxylic acid halide, etc. can also be used.

Compounds with hydroxyl groups include methanol, ethanol, propatool, butanol, hexanol,
Monohydric alcohols such as octatool, nonanol, decanol, dodecanol, tridecanol, tetradecanol, hexadecanol, octadecanol, icosanol, oleyl alcohol; ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, polyglycerin , trimethylolpropane, pentaerythritol, sorbitol, glucose, sucrose, cellulose, starch, saponified products of polyvinyl acetate, polyhydric alcohols such as triethanolamine; phenol, cresol, xylenol, octylphenol, nonylphenol, dodecylphenol, resorcinol In addition to phenols such as , catechol, hydroquinone, pyrogallol, and caftol, they include castor oil, hydrogenated castor oil, and fatty acid jetanolamide. Also included are condensates of the aforementioned phenols with formaldehyde.

Examples of compounds having a thiol group include butyl mercaptan, ethyl mercaptan, butyl mercaptan, octyl mercaptan, dedyl mercaptan, dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, ethanedithiol, and the like.

Examples of compounds having an amino group or imino group include methylamine, ethylamine, butyviramine, hexylamine, octylamine, decylamine, dodecylamine,
Monovalent amines such as hexadecylamine, octadecylamine, t-allylamine, oleylamine, coconut oil alkylamine, tallow alkylamine, cyclohexyldiamine, benzylamine, aniline, toluidine; propylenediamine, hexamethylenediamine, tallow alkylpropylenediamine , cyclohexyldiamine, phenylenediamine, benzidine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, and other polyvalent amines; oxyamide, acetamide, capric acid amide, caprylic acid amide, capric acid amide, lauric acid These include fatty acid amides such as 7amide, myristic acid amide, valmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, and erucic acid amide.

Compounds with carboxyl groups include formic acid, acetic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, valmitic acid, stearic acid, behenic acid, 2-ethylhexanoic acid, isostearic acid, oleic acid, Erucic acid, oxalic acid, malonic acid, co/phosphoric acid, glutaric acid, adinic acid, azelaic acid, sebacic acid 1.
Aliphatic carboxylic acids such as dodecanedioic acid, maleic acid, dimer acid, butanetetracarboxylic acid, ethylenedi7minetetraacetic acid; benzoic acid, toluic acid, phthalic acid, phenylacetic acid, cinnamic acid, hemimellitic acid, trimellidic acid, trimesine Aromatic carboxylic acids such as acid, bimellitic acid; polymerized carboxylic acids such as polyacrylic acid, polymethacrylic acid, and maleic acid copolymers.

In addition, compounds with two or more different active hydrogen groups include lactic acid, glyfuric acid, malic acid, tartaric acid, thioglycolic acid, glycine, N-fulkylchrysine, monoethanolamine, jetanolamine, and amine ethylethanolamine. , salicylic acid, gallic acid, aminobenzoic acid, etc.

Examples of polyvalent incyanates for crosslinking polyether compounds include hexamethylene diisocyanate, tolylene diisocyanate, metaxylene diisocyanate, L5-
There are naphthylene diisocyanate, 44+-diphenylmethane diisocyanate, etc. Polyvalent epoxides include diglycidyl bisphenol A1 diglycidyl ethylene glycol, diglycidyl tetraoxyethylene glycol, etc. Polyvalent carboxylic acids include oxalic acid, malonic acid, and succinic acid. , glutaric acid, 7-divic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, butanetetracarboxylic acid, 7-talic acid, etc., and examples of the polycarboxylic acid no-ride include the above-mentioned polycarboxylic acid pastes. There is also Plumid.

Further, bituminous substances include coal tar, coal tar pitch, and petroleum pitch.

The surfactant, which is a stabilizer, is added in an amount of 0.401 to 2% by weight, preferably 0.03 to 0.5% by weight, in the mixed fuel. The effect is small in the 001 weight/weight groove, and the effect does not improve much even if it exceeds 2% by weight.

The bituminous substance as a stabilizer is 1:: 0.1-5 in the mixed fuel.
It is added in an amount of 0.5 to 3% by weight, preferably 0.5 to 3% by weight.

If it is less than 0.1% by weight, the effect will be small, and if it exceeds 5% by weight, the stability will improve, but the viscosity of the mixed fuel will increase, which is not preferable.

Surfactants and bituminous substances may be used in combination.

The amount of coal powder in the mixed fuel composition according to the present invention is 30 to 70% by weight, preferably 50 to 65% by weight, excluding the water contained therein.

Coal usually contains a certain amount of moisture, sometimes as much as 40%.
May contain 0% by weight. If the coal contains a large amount of moisture, it is preferable to dry the coal to reduce the moisture content to 15% by weight or less, preferably 10% by weight or less. Too much water will affect the transportation efficiency and fuel efficiency of the mixed fuel, preferably 25 to 50% by weight.

Although the method for producing the mixed fuel composition of the present invention is not particularly limited, it can be produced, for example, in the following manner.

Dry or wet pulverized coal adjusted to have the particle size distribution of the present invention, fuel oil, and a stabilizer are simultaneously mixed using a propeller-type stirrer or the like, and then a high-speed mixer that applies high shear force, such as a homogenizer, is used. After wet pulverization by adding a predetermined amount of coarsely pulverized coal, fuel oil, and stabilizer into a wet ball mill having a ball particle size distribution adjusted to the particle size distribution of the present invention, There is a method of stirring using a high-speed mixer r having high shearing force. Also, in this case, the stabilizer may be added after the coal is pulverized in the fuel oil.

Next, the present invention will be explained by examples.

The rod penetration test shown in the examples was conducted as follows.

As a test device, a washer with an inner diameter of 5.5α and a height of 20 mm was placed on top with a guide hole in the center, and the time taken to reach the bottom of the tip of the diameter 5 mm was measured through the center guide hole. It was defined as the rod penetration time. This is a mixed fuel with excellent stability as there is little sedimentation and consolidation of the seed coal powder, which takes a short time. In addition, if the glass rod stopped halfway before reaching the bottom, the height from the stopped position to the bottom was expressed as the sedimentation consolidation layer. Further, the rod penetration test and the viscosity measurement were both carried out at 70C.The Australian bituminous coal and Middle Eastern heavy oil C used in the examples had the following properties.

Australian bituminous coal specific moisture = 2.44% by weight Fixed carbon 54% by weight Fuel ratio: 156 Ash content: 134% by weight HGI: 51 Calorific value of C heavy oil from the Middle East: 1 o 310 Kcal/9 specific gravity:
0.9576 Pour point knee 2.5C Moisture: 0.03% by weight Elemental analysis: C: 84.17% by weight H: 13.06% by weight S: 239% by weight N: 0.25% by weight 0: 0.13 Weight% Example: Australian bituminous coal was dry-pulverized in a cage mill, and Q
, 5 g + i and 0.1 m screen to obtain two types of fine coal powder samples, and by these blends, A-1 to A-3 (particle size distribution of the present invention) and B-1 shown in Table 1 were obtained.
Coal powder samples of ~B-3 (particle size distribution other than the present invention) were obtained. The moisture content of both of these samples was 1%. These coal powder samples were mixed with C heavy oil from the Middle East and a stabilizer.
A mixture of
Mixed fuel composition shown in Table 2 (present invention: A1~/FIl
i6, comparison = A7 to black 12) was obtained. Table 3 shows the viscosity of these mixed fuel compositions at 70C (by B-type viscometer).
It also shows the rod penetration time after being left at 70C for 4 weeks, and it is clear that the mixed fuel composition of the present invention has a low viscosity and good stability.

Claims (1)

[Claims] 1. In a mixed fuel composition consisting of coal powder, fuel oil, and stabilizer, the cumulative weight percentage of coal powder particle size is 150
0μ or less: 100chi, 300P or less: 95~ioochi,
200P or less = 80-90%, 100P or less = 55-7
5%, 10μ or less = 15-35% 11μ or less = 3-10
%.