JPS60192793A - Coal/alcohol fuel in slurry - Google Patents

Abstract

PURPOSE:To provide a fuel suitable for pipe line transport and excellent in storage and transport stabilities, prepd. by adding to a coal/alcohol slurry a polymer which contains sulfonated unsatd. aromatic compd. as a structural unit. CONSTITUTION:The fuel is prepd. by adding 0.005-3wt% at least one acid (or salt thereof) consisting of a polymer which contains, as monomer unit, 30wt% or higher sulfonated aromatic compd. with reactive C=C unsatd. bond and has a number-average M.W. of 800-50,000, to a slurry consisting mainly of a mixt. of powdered coal and alcohol. Preferred reactive C=C unsatd. bond-contg. aromatic compds. are styrene, alpha-methylstyrene, vinylnaphthalene, coumarone and indene.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coal-alcohol slurry fuel with excellent flow characteristics for pipeline transportation and combustion.

In recent years, many studies have been conducted on the handling of fO3 coal to use it as fuel. For example, powdered coal is dispersed in fuel oil or water to form a slurry.

This is being transported by pipeline, but
The amount of coal in PJ was as low as 20-401.

There are problems such as a decrease in calorific value during combustion, and cost reduction has not yet been solved.

As a way to overcome the above-mentioned deficiencies, a mixed fuel of powdered coal and alcohol is attracting attention.

However, if powdered coal and alcohol are simply mixed, a satisfactory mixed fuel cannot be obtained because the powdered coal settles and separates due to the difference in specific ratio, condenses, and loses fluidity.

Therefore, it is also possible to find additives that have the same stability as above.
This is one of the most expensive issues and an example is Japanese Patent Application Laid-Open No. 57-14939.
An example of this can be seen in 1st place.

Even when a slowing agent of 1% by weight or more is used, the vibration stability required for ship transportation etc. is poor and practical application will be short-lived.

In JP-A-53-55304, it has been shown that a flammable pseudo-syquinetropic suspension can be obtained by dispersing pulverized coal in which most of the coal particles are 100 mesh or less in methanol. . The suspension can be maintained in a suspended state by only mild agitation during storage, and it is also controlled to prevent separation when pumped through pipelines, and has shear thinning-rheological properties and is quiet. It has an apparent viscosity lower than that of the liquid and can be transported by pump. However, if the stirring is stopped, a part of the suspended pulverized coal σ) will settle at the bottom of the storage container, forming a hard layer of coal, a so-called consolidation layer. This consolidated layer is 1
In some cases, it is possible to restore fluidity by performing strong agitation H', but in some cases it is difficult to recover the original amount, so transportation and storage of the suspension from the production field to the consumption area is difficult. When you think about it, it poses a huge technical and economical problem, and it is unlikely that it will be practical.

In the case of a colloidal suspension in which the coal particles are small and maintain a suspended state, sedimentation and separation are difficult to occur and stability is good, but pulverization costs are high and However, it is difficult to obtain a fine powdered coal-alcohol suspension due to its high viscosity, which makes pumping difficult.

A suspension made by simply mixing powdered coal and alcohol becomes noticeably thicker when the carbonic acid content is increased.

Due to the loss of fluidity, pipeline transportation and jet combustion become difficult, and lowering the coal & After careful consideration to overcome the defects,
The present invention was achieved by discovering that by using an additive with a specific structure, it is possible to reduce viscosity and obtain excellent flow characteristics for pipeline transportation and combustion.

One aspect of the present invention is to use a sulfonated reactive carbon-carbon seasoning agent in a coal-alcohol slurry fuel mainly consisting of a mixture of powdered coal and alcohol.
Contains at least 30% by weight of an aromatic compound having a bond as a monomer constituent unit? :0.005~3
This is a coal-alcohol slurry IJ-like mN characterized by containing M in a range of M amount.

According to the present invention, a coal-alcohol slurry fuel 711iH, which is effective in reducing the viscosity and having excellent fluidity characteristics for pipeline transportation and combustion, is produced by using the above-mentioned specific heavy additive (1). .

The above-mentioned reactive carbon-carbon unsaturated bond aromatic compounds include styrene, α-methylstyrene,
β-methylstyrene, 0-methylstyrene.

Styrene derivatives such as m-methylstyrene, P-methylstyrene, p-n butylstyrene, 2,6-dimethylsterene, α-chlorostyrene, stilbene, α-vinylnaphthalene, β-vinylnaphthalene, 4-1ertbutyl-1- Vinyl naphtha 1/n.

Vinylnaphthalene fatty conductors such as 7-methyl-l-vinylnaphthalene, acetylene derivatives such as phenylacetylene, P-tolylacetylene, and 1,2-diphenylacetylene, 2-vinylpyridine, coumaron, indene, etc. are useful and preferred. Specifically, styrene, α-methylstyrene, vinylna-2-talene.

They are Kumaron and Inden. Also, as an aromatic compound that cleaves a reactive carbon-carbon vesicle 5fD bond in which a sulfone group is introduced into the aromatic nucleus in advance, what are the following? l! For example, sodium P-styrene sulfonate, ammonium O-styrene sulfonate, methylamine salt of l-vinylnaphthalene-4-sulfonate, and the like are useful.

An example of the polymer according to the present invention is polystyrene, which is obtained by polymerizing an aromatic compound bearing a reactive carbon-carbon unsaturated bond as a monomer component and then sulfonating the aromatic nucleus.

Homopolymer of polyvinylnaphthalene and coumaron.

Indene homopolymer, coumaron-indene copolymer, styrene-indene copolymer, α-methylstyrene-
Polymer 1 obtained by polymerizing an aromatic compound having a reactive carbon-carbon unsaturated bond in which a sulfone group is attached to the aromatic nucleus in advance, such as vinyl toluene or a sulfonated product of tt41.
For example, P-styrene sulfonic acid (IJ) homopolymer, P-styrene sulfone ammonium α
-Methylstyrene copolymers and the like are useful.

Furthermore, Ishikawa also includes car body bodies obtained by copolymerizing aromatic compounds having reactive carbon-carbon unsaturated bonds as described above with other car body compounds, and polymers obtained by copolymerization and sulfonation. .

Examples of other undercarriage compounds used as monomer components of the copolymer include vinyl chloride, HI-
Vinyl acid, butadiene, acrylic acid, methyl acrylate, isopropyl acrylate, acrylic esters such as inbutyl acrylate, methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Methacrylic acid esters such as 4-ethyloctyl, maleic acid, fumaric acid, dimethylmaleic acid, diethylmaleic acid,
σ) Maleic acid derivatives such as dimethyl maleate.

Itaconic acid, itaconic acid derivatives such as methyl itacoate, diinbutylene, imbutylene, 1-butene, 1-pentene, 2-methyl-1-butene.

3-methyl-1-butene, l-hexene, l-heptene, l-octene, l-nonene, l-1-tetradecene, l
-α-olefins such as hexatecene.

Useful include, but are not limited to, cyclopentadiene, atarylonitrile, methacrylonitrile, acrylamide, and methacrylamide.

The content of the aromatic compound containing the sulfonated reactive carbon-carbon group, which is a heptamer structural unit in the polymer, is at least 30 units, preferably 40 units or more. It is. This is considered to be because if the M-containing lid is less than 30% by weight, the hydrophobicity becomes strong and the dispersion effect of coal particles in the slurry fuel becomes small. Further, the number average molecular weight of the final sulfonated vehicle body may be determined to be 800 to 50,000, preferably 1,000 to 20,000; if the molecular weight is less than 800, a sufficient dispersion effect of the coal particles cannot be obtained; -Those exceeding 150,000 have poor solubility in methanol and are difficult to use commercially.

Special additives used in the coal-alcohol slurry fuel of the present invention are the above-mentioned sulfonated acids and/or their salts, preferably 1
is monovalent, divalent or 31-valent metal salt, ammonium salt or amine salt. These salts may have an excess of either the acid or the base, and may be used after the reed salt is prepared, or the acid and the base to be paired may be used separately.

Metals that form salt include lithium, sodium, potassium, magnesium, calcium, zinc, cadmium, barium, aluminum, and lead.

Tin, copper, chromium, mankan, iron, cobalt, nickel, etc. are useful.

Examples of amines that form salts include alkylamines, alkanolamines, aromatic amines, pyridine and its derivatives, and quaternized N'kW compounds, such as methylamine, ethylamine, butylamine, octylamine, and lauryl. Amine.

stearylamine, oleylamine, dimethylamine,
N-methyl-laurylamine, dilaurylamine, trimethylamine, N,N-dimethyl-laurylamine, monoethanolamine, jetanolamine, triethanolamine, monoimpropaturamine, diinglobanolamine.

Tri-inpropaturamine, ethylenediamine.

Hexamethylenediamine, diethylenetriamine.

Gyutoki alkylamine, morpholine, aniline, p-toluidine, m-toluidine, nitroaniline.

Benzylamine, cyclohexylamine, pyridine, phenylenediamine, benzidine, cyclohexyldiamine, and the like are useful.

The sulfonated compound and the salts thereof are known compounds and can be produced by known methods, and contain aromatic compounds containing reactive carbon-carbon bonds as monomer components. A polymerizable compound containing a group compound is polymerized by a conventional method, for example, in the presence of a polymerization catalyst such as tert-butyl peroxide or asobisin butyronitrile, or a polymerization control agent such as carbon tetrachloride. It can be obtained by sulfonating an aromatic nucleus with a sulfonating agent such as sulfuric anhydride, and then by a salt formation reaction.

It is also possible to similarly polymerize a polymerizable compound containing an aromatic compound having a reactive carbon-carbon bond in which a sulfone group is attached to the aromatic nucleus in advance, but the present invention is not limited to these. do not have.

Further, the addition value of the specific additive used in the coal-alcohol slurry fuel of the present invention varies depending on the type of coal, particle size distribution, etc., but generally it is 0.005 to 3 to the total weight of the slurry fuel. weight%.

Preferably, the proportion is in the range of 0.01-1% by weight. If the amount added is less than 5% by weight, it is not suitable because it is difficult to obtain a sufficient fluidity effect, and if it exceeds 3% by weight, it is not economically disadvantageous, but on the contrary, it may impair the fluidity and cause problems. This is not preferable because it does not provide the flat physical properties of the coal-alcohol slurry fuel of the invention.

The present additive may also be used as a thinner, such as a salt consisting of an unsaturated acid such as acrylic acid or a copolymer thereof.

Fatty acid groups such as quene Tg&, partially desulfonated lignin sulfonate obtained by desulfonating lignin sulfonic acid, anionic surfactants such as naphthalene sulfone and salts consisting of formalin condensates of petroleum sulfonic acid, amines, At least one active hydrogen in the molecule, such as ionic compounds such as condensed phosphates, carbonates, etc., stabilizers such as evacarbonates, alcohols, amines, polypropylene glycols, and compounds with phenolic water groups. M
Depart the compound to! ? Nonionic surfactants such as alkylene/oxide adducts with an ethylene oxide content of 80% by weight or more and a number average molecular weight of 1,000 to 10,000, as well as Wbtit esters and phosphoric acids. Esterified product, N, N.

It may be used in combination with an amphoteric surfactant such as N-distearyl methyl ammonium betaine, an inorganic substance such as ultrafine silica, carbon black, bentonite, etc.

The additive of the present invention may be used alone, but in order for it to function effectively, a diluent, such as water, must be added in advance.

It is preferable to use one solution in lower alcohols, acetone, toluene, and mixtures thereof.

The addition method may be, for example, adding it during wet pulverization of a mixture of coal and alcohol, or adding it at the time of pulverizing coal or mixing pre-pulverized coal and alcohol, or after mixing. The bundle of the present invention can also be achieved by a method.

The powdered coal used in the coal-alcohol slurry fuel of the present invention is pulverized coal of at least one type selected from anthracite, m-blue coal, sub-green coal, and lignite. Any material can be used, regardless of origin, cultural composition, or moisture content.

Also, regarding the size of coal particles, regardless of the size of one particle.

By using the carefully selected 6≦additive of the present invention, the viscosity Z is lowered and the flow characteristics of pipeline transmission and combustion are excellent. However, one coal particle is 4 mesh or less,
In order to achieve the object of the present invention, it is particularly preferable that most of these particles have a size of 16 meshes or less. What is the amount of this powdered coal mixed?

30~ for final coal-alcohol slurry fuel
It is preferable to have a weight of 80 tons, and if powdered coal exceeding 80 weight percent is mixed with alcohol, the viscosity will be noticeably higher and the fluidity will be lost. If you mix both types.

Coal-alcohol slurry fuel Q) The coal-alcohol slurry fuel of the present invention is not favorable because it does not have a low degree of fineness, and the physical properties of the coal-alcohol slurry fuel of the present invention cannot be obtained.

Therefore, S regular 30-80 Yu Kei, preferably 40-7 for history
The range is 0 tons.

In addition, the coal-alcohol slurry fuel of the present invention includes:
For the final coal-alcohol slurry state 7#+, less than 30% water molecules by weight can be mixed. If the moisture content exceeds 311%, transportation costs, storage costs, and other general and administrative costs for the coal-alcohol slurry fuel will be reduced.1C.In addition, heat loss due to the heat of evaporation of water during combustion will increase1. Therefore, the object of the present invention cannot be achieved. still.

The meaning of water in the coal-alcohol slurry fuel is:
It can be optimized depending on the purpose, but for example, in order to reduce NOx and soot in combustion exhaust gas,
It is preferable to contain 5 to 10 parts of water by weight. Moisture is usually provided by the moisture in the coal, but it can be added separately or selected as appropriate by the operator.

The alcohol used in the coal-alcohol slurry fuel of the present invention is at least one of lower aliphatic alcohols having 1 to 4 carbon atoms, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, 1 SO-propyl alcohol, n-butyl alcohol, tert-butyl alcohol, ethylene glycol, phlopylene gelicol, etc. 1C contiguity and physical properties! l) Methyl alcohol is particularly preferred, and the alcohol may also contain a chemical bathing agent, an organic compound such as water, or an inorganic compound that is included during industrial production.

The coal-alcohol slurry fuel according to the present invention has a low viscosity (excellent flow characteristics), and can be easily transported by pipeline and spray-combusted.

Further, the uninvented coal-alcohol slurry fuel has a remarkable difference in ash dispersion between the upper and lower layers after being left still, and it becomes possible to separate the ash from the coal-alcohol. This is because the additives used in the slurry fuel are adsorbed to the coal particles in the slurry and dispersed in the slurry by imparting an electric charge, and the ash content in the coal particles is
This is thought to be due to coagulation and sedimentation.

Next, the unexploded BA will be explained in detail using an example.

Example 1 207 tons of methyl alcohol, 3 g of sodium polystyrene sulfonate (molecular weight: 2,000, sulfonic group introduction rate: 90%), and 305 tons of water were placed in a beaker with a capacity of 11,000 kg, and mixed at room temperature using a homomixer at 110 kg.
The mixture was stirred and mixed for 10 minutes under the condition of 0 Orp.

Next, powdered sub-bituminous coal (100 mesh: L passing through 97.5 weight units, 200 mesh passing through 75.2 weight percent, 350 mesh passing through 53.6 weight percent, water content 50 weight percent, ash content 14 B)
Weight %) 36 (l) and stirred for 2θ minutes at 1000 rpm to prepare coal-alcohol solution!j-60Of
I got it.

The viscosity (*l) of this product was 2100CP. Next, a deashing property (ash content) test (*2) was conducted on the Shaolai 8 coal ash content, which was 11.0% by weight for upper layers and 11.8% by weight for middle layers.
, the lower layer was 19.9% by weight, and the difference in ash content in the coal between the upper and lower layer samples was significantly large. This coal-alcohol slurry fuel, whose main component is a mixture of coal and alcohol, has low viscosity (excellent fluidity, easy pipeline transportation and spray combustion, and 1) good deashing properties. It was something.

(*l) Viscosity measurement The viscosity was measured using a double cylindrical viscometer (manufactured by The Hague, Rotor MVU) at a liquid temperature of 20° C. and a rotation speed of 5 rpm.

The lower the viscosity of the slurry fuel, the better the fluidity.

- (1 * 2) Demineralization (ash content Ji) test Pour the above coal-alcohol slurry fuel into a 500d measuring cylinder (inner diameter 50m/m) in an amount of 500mm and let it stand at room temperature for 3 days. . After standing still for some time, the upper 170 m of the slurry fuel in this cylinder was taken out and an upper layer sample was taken.
mg'i medium increase sample, lower 5160 tnl is the upper layer sample. The coal content of these samples was measured according to JISM8812. The larger the difference in the ash content in the coal between layers, the better the deashing performance. Coal-alcohol slurry fuels containing coal and alcohol as main components were prepared by varying the amount of addition. The viscosity and demineralization properties of these are shown in Table 1. In addition, cases in which additives other than the additives of the present invention were used are also listed in Table 1 as comparative examples. Table 2 shows the properties of the coal used in the Examples and Comparative Examples.

As shown in Table 1, the coal-alcohol slurry fuel according to the present invention has low viscosity and fluidity characteristics for pipeline transportation and combustion by using specific σ) additives, regardless of whether it is charcoal or alcohol. It was found that it had excellent effects and also had good demineralization properties.

Claims (3)

[Claims] (1) In a coal-alcohol slurry fuel mainly composed of a mixture of powdered coal and alcohol, the monomer constituent unit is an aromatic compound that is sulfonated and becomes reactive carbon-carbon. as at least 3
Coal-alcohol ν) Sura IJ characterized by the fact that the number average molecular company that contains 0 heavy demon attacks falls within the range of 3 car volume.
-State N. (2) The first claim is an aromatic compound having a reactive carbon-carbon disarticulated bond, or styrene, α-methylstyrene, vinylnaphthalene, coumaron, or intene.
Coal-alcohol slurry fuel as described in Section 3. (3) The coal-alcohol θ) slurry fuel according to claim 1 or 2, wherein the counter ion forming the salt is monovalent, divalent, or trivalent metal oxide, ammonium, or amine. .