JPS62181393A - Coal-water slurry composition - Google Patents

Abstract

PURPOSE:A coal-water slurry composition, containing a dispersing agent consisting of a polymer of a sulfonated substance, assistant consisting of a hydroxycarboxylic acid, etc., coal and water at a specific ratio and having improved fluidity and storage stability. CONSTITUTION:A coal-water slurry composition, containing (A) a polymer prepared by polymerizing one or more sulfonated substances selected from the group consisting of (i) a sulfonated 9-12C norbornene having 2 double bonds in the molecule, (ii) a sulfonated 8-12C cyclohexane derivative having 2 double bonds in the molecule and (iii) a sulfonated 4-7C aliphatic diene, (B) one or more compounds selected from hydroxycarboxylic acid (salt), polyphosphoric acid (salt) and organic chelating agent, (C) coal and (D) water and obtained by blending 100pts.wt. component (C) with 0.01-10pts.wt. component (A) and 0.001-2pts.wt. component (B).

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides a flowable,
The present invention relates to a coal-water slurry composition with excellent storage stability.

<Prior Art> In recent years, due to the depletion of petroleum resources, the use of coal has been rediscovered, and various ways of using it have been studied.

However, since coal is solid unlike liquid fuels such as petroleum, it has poor handling properties, and this drawback has limited its use.

For this reason, various techniques have been proposed in which coal is pulverized, dispersed in water, and treated as a slurry in the same way as a liquid. In this case, it is possible to obtain a slurry with a low viscosity by lowering the coal concentration in the slurry and using a large amount of water, but this is not a good idea in terms of fuel efficiency. Furthermore, the slurry thus obtained has the disadvantage that the coal settles during storage.

As a method to increase the coal concentration in slurry.

A method has been proposed in which various dispersants are added to the slurry to improve the dispersibility of coal in water.

<Problems to be solved by the invention> Highly concentrated coal-water slurry, which is produced by pulverizing coal and dispersing it in water, is generally transported, stored, and used as fuel, so it is not stable over a long period of time as a slurry. It is required that the liquid be present in a large amount of water and have high fluidity.

However, coal, which is a raw material, contains various impurities, and their types and contents are difficult to determine.

It varies greatly depending on the coal production area, coal type, etc.

For this reason, it has been difficult to supply a highly concentrated coal-water slurry composition that has long-term stability and high fluidity, regardless of the properties of the coal.

The object of the present invention is to provide a highly concentrated coal-water slurry composition that has long-term stability and high flowability, regardless of the properties of the coal.

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned conventional technical problems, the present inventors have found that the properties of one coal can be improved by using a specific dispersant and a specific auxiliary agent together. We have discovered that it is possible to obtain a highly concentrated coal-water slurry composition with extremely excellent stability and fluidity without being affected, and have arrived at the present invention.

That is, one aspect of the present invention is.

(a) As a dispersant, a sulfonated product of a norbornene derivative having 9 to 12 carbon atoms containing two double bonds in one molecule and/or a 8-carbon derivative containing two double bonds in the molecule
~12 cyclohexene derivatives sulfonated products and/
Or a polymer obtained by polymerizing a sulfonated aliphatic diene having 4 to 7 carbon atoms.

(b) Coal-water slurry with excellent dispersion stability even at high concentrations, characterized by containing at least one selected from hydroxycarboxylic acid and/or its salt, polyphosphoric acid and/or its salt, and an organic chelating agent. A composition is provided.

The norbornene derivative used as a starting material for a dispersant is a norbornene derivative with 9 to 12 carbon atoms that contains two double bonds in the molecule (however, the norbornene ring contains one double bond), and is usually General formula (A), (B)
It is a dicyclopentadiene derivative represented by (C).

R1 (wherein, Ro and R2 are alkyl groups having 1 to 4 carbon atoms or hydrogen atoms, R3 and R4 are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, R9 is an alkylene group having 1 to 3 carbon atoms, RG
, R is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom,
R, 1, and R represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; 0 represents 0 or 1; ) In addition, in the general formulas (A) and (13), R2R
.

is located at the 6th position, but may also be located at the 5th position.

The norbornene derivatives represented by the above general formulas (A), (r3) and (C) are produced by cyclopentadiene as the diene component, Diels-Alder reaction with dienes having 4 to 7 carbon atoms, and naphtha as the genophile component. It can be obtained by pyrolysis etc.

Examples of diene components having 4 to 7 carbon atoms used as genophile components include 1,3-butadiene, 1,2-butadiene, 1,2-pentadiene, 1,3-pentadiene, 2,3-pentadiene, isoprene, and cyclo. Pentagen.

1.2-hexadiene, 1,3-hexadiene, 1.4
-Hexadiene, 1,5-hexadiene, 2,3-hexadiene, 2,4-hexadiene, 2,3-dimethyl-
1,3-butadiene, 2-ethyl-1,3-butadiene, methylcyclopentadiene, 1,2-hebutadiene,
1,3-hebutadiene, 1,4-hebutadiene, 1,5
-hebutadiene, 1,6-hebutadiene, 2.3-heptadiene, 2.5-headadiene, 3.4-hebutadiene, 3.5-hebutadiene and 1 branched carbon number 4-7
These are various dienes.

When cyclopentadiene and the genophile component undergo a Diels-Alder reaction, a norbornene derivative is produced in which double bonds other than the double bond of the norbornene ring having 9 to 12 carbon atoms and the double bond that acted as genophile remain.

A typical example of this is 5-vinyl-norbornene-2,5-ethylidene-norbornene-2,5-methylene-6-methylnorbornene-2,5-propenyl-norbornene-2゜5-vinyl-6- Methylnorbornene-2,5-isopropenyl-norbornene-2,5
Examples include -methyl-5-vinyl-norbornene-2,5-allyl-norbornene-2,5-vinyl-6ethylnorbornene-2,5-butenyl-norbornene-2 and dicyclopentadiene.

Next, the cyclohexene derivative has two double bonds in the molecule.
It is a cyclohexene derivative having 8 to 12 carbon atoms (however, the cyclohexene ring contains one double bond), and is usually represented by the general formula (D), (E) or (■?).

R1,.

R84 (In general formulas (D), (E), and (F), R1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R1□
, r<□1, Rt4 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Rts is an alkylene group having 1 to 4 carbon atoms, R1
R17 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
0 is O or 1. ) In the present invention, R1□R1 in general formulas (l) and (E) is at position 4, but may be at position 5).

The cyclohexene 1 derivative has (+′)) as a component,
1,3-butadiene, 1. ; Conjugated diene having 4 to 6 carbon atoms such as 3-pentadiene, isoprene, 1,3-hexadiene, 2゜3-dimethylbutadiene; as component (E), in addition to the conjugated diene of component (D), 1, 4 such as 2-butadiene, 1,4-pentadiene, cyclopentadiene, etc.
This is a product obtained when Diels-Alder reaction is performed with the dienes of 6 to 6, with the diene as the component (D) and the genophile as the component (E).

To give a specific example, 4-vinyl-cyclohexene-1
,4-vinylidene-cyclohexene-1,4-ethylidene-cyclohexene-1,4-methylene-5-cyclohexene-1,4-isopropenyl-cyclohexene-1
,4-isopropenyl-6-methyl-cyclohexene-
1゜4-propenyl-cyclohexene-1,4-propenyl-6-methyl-cyclohexene-1,4-vinyl-
5-Methyl-cyclohexene-1,3-methyl-4-vinyl-cyclohexene-1,4-methyl-4-vinyl-
Cyclohexene-1゜4-butenyl-cyclohexene-
1, tetrahydroindene, 7-ituprobenyl-cyclohexene-1,1-methyl-4-propenyl-cyclohexene-1, and the like.

In addition, examples of aliphatic dienes having 4 to 7 carbon atoms (hereinafter sometimes referred to as "aliphatic dienes") containing two double bonds in the molecule include 1°3-butadiene, 1.2-
Butadiene, 1,2-pentadiene, 1,3-pentadiene, 2,3-pentadiene, isoprene, 1,2-hexadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2.3-hexadiene,
2,4-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1°3-butadiene, 1,2-
Hebutadiene, 1゜3-heptadiene, 1,4-hebutadiene, 1゜5-hebutadiene, 1,6-hebutadiene, 2゜3-hebutadiene, 2,5-hebutadiene, 3゜4-hebutadiene , 3,5-heptadiene, etc.
Examples include various branched dienes having 4 to 7 carbon atoms.

These aliphatic dienes can be used alone or in combination of two or more.

Various methods can be used to produce the sulfonated derivatives or dienes. For example, they can be produced by sulfonating a double bond by the method shown below.

That is, the sulfonation reaction applied to unsaturated compounds, especially unsaturated aliphatic or unsaturated alicyclic compounds, is described in the book "Sulfonation and Related Reactions J" by Gilbert (E, IE, G11bert).
Re1ated Reaction), Interscience Publishers Incoholated (In
tcrscience Publishers Inc.
) (1965), and Charles J.
Norton et al., The Journal of Organic Chemistry
rganic chemistry) 4158 pages (19
Sulfonation can also be achieved by the addition reaction of sulfites to unsaturated bonds, as shown in the study of 1968).

As the sulfonating agent in this case, acidic sulfites, metasulfites, or sulfites of alkali metals are usually used alone or as a mixture.

In addition, the cation species of the sulfonated product obtained are as follows.

Although not particularly limited, hydrogen, alkali metals, alkaline earth metals, ammonium, amines, and the like are preferred in order to make them water-soluble.

Examples of the alkali metal include sodium and potassium, and examples of the amine include alkylamines such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, triethylamine, butylamine, dibutylamine, and tributylamine, ethylenediamine, diethylenetriamine, and triethylenetheramine. Examples of alkaline earth metals include polyamines such as morpholine and piperidine, and examples of alkaline earth metals include calcium and magnesium.

Additionally, these cations can be interchanged with other cation species by various ion exchange techniques.

Next, the polymer of the sulfonated derivative or diene used as component (a) of the present invention is a polymer obtained by polymerizing at least one of the sulfonated derivative or diene. , or a polymer obtained by copolymerizing the above-mentioned derivatives or sulfonated dienes with a polymerizable monomer (hereinafter referred to as a "comonomer").

The method for producing this polymer is as follows.

For example, a derivative or a sulfonated diene, or a comonomer thereof and a comonomer thereof are reacted in the presence of an acidic compound catalyst at a reaction temperature of usually -20 to 300°C, preferably 80 to 180°C for several hours. A polymer can be produced by carrying out a polymerization reaction for several tens of hours. In the polymerization reaction, a solvent for the polymerization reaction can be used in order to carry out the reaction smoothly, and the solvent for the polymerization reaction may include polar solvents such as water, hydrocarbons, halogens, etc., as long as it does not hinder the polymerization reaction. Any material such as carbonized hydrocarbons can be used.

The acidic compound catalysts include sulfuric acid, phosphoric acid, hydrogen fluoride, boron fluoride and its Y form, aluminum chloride t1
Examples include Lewis acids such as aluminum pentabromide, tin tetrachloride, dichlorochloride (lead), titanium trichloride, and organic proprotic acids.

Among them, sulfuric acid can be cited as a typical example.

Examples of copolymerizable monomers include aliphatic, alicyclic, and aromatic hydrocarbons having an olefinic divalent bond, unsaturated amino acids,
Unsaturated alcohol, unsaturated ester, unsaturated di-1-lyl, unsaturated carboxylic acid and its ester, unsaturated sulfonic acid and its ester, etc., or aliphatic, alicyclic,
One or more aromatic alcohols or phenols, or alcohols or diols having an amino group, an ester group, a di-1-lyl group, a carboxylic acid group, or a sulfonic acid group can be used in any proportion.

By changing the Nl of the copolymerized monomer used,
The surfactant properties of the polymer can be altered.

To suppress foaming when a polymer is produced from the sulfonated product of the present invention and a comonomer and used as a dispersant for coal.

The weight of the polymer is at least 50% by weight, preferably at least 70% by weight.

The molecular weights of the polymers and copolymers obtained by the present invention can be changed as appropriate by the reaction conditions, particularly the type and amount of the acidic compound catalyst, the type and amount of the solvent, or the reaction temperature and reaction time.

When the polymers and copolymers thus obtained are used as the dispersant of the present invention, it is preferable that the weight i "l' average distribution amount is north of 500, more preferably 1
．． 000 or more, and 2°000 to 100,000 is particularly preferable.

Furthermore, the sulfonated polymers and copolymers can be mutually exchanged into acid forms or salts of alkali metals, alkaline earth metals, ammonium, amines, etc. by ion exchange methods or neutralization reactions.

Next, as the hydroxycarboxylic acid or its salt which is the component (b) of the present invention, chain hydroxycarboxylic acids such as tartronic acid, lactic acid, gluconic acid, malic acid, tartaric acid, citric acid, and grape acid, or salicylic acid, etc. Examples include aromatic hydroxycarboxylic acids or salts thereof. In addition, as polyphosphoric acid or its salt, pyrophosphoric acid, l-
Examples include lyphosphoric acid, trimetaphosphoric acid, 1-rametaphosphoric acid, hexametaphosphoric acid, I-ribolyphosphoric acid, or salts thereof. Examples of the organic chelating agent include aminocarboxylic acids or salts thereof such as ethylenediaminetetraacetic acid, iminodiacetic acid, and nitrilotriacetic acid. In addition, the cations that form the salt include sodium, potassium,
Examples include metals such as calcium, ammonia, amines, and quaternized amines.

The coal used in the present invention is determined by its origin, ash content, lignite, subbituminous coal, il! It is not limited by the type of coal such as blue coal or anthracite.

It goes without saying that demineralized and refined coal may be used.

The dispersant, which is the component (a) of the present invention, can be used in combination with one or more kinds of anionic surfactants, nonionic surfactants, etc., which will be described later, if necessary, and can be used at a concentration of 50%, although not particularly limited.
The amount of component (a), which is a dispersant added to ~85% by weight high-degree coal-water slurry, should be selected in accordance with the desired viscosity, as the viscosity of the slurry decreases as the amount increases. It can be used in an amount of usually 0.01 to 10 parts by weight per 100 parts by weight of coal (c), but preferably 0.05 to 2 parts by weight from the viewpoint of workability and economy.

The amount of component (b) in the present invention is determined by the amount of impurities contained in the coal (2).
The amount of ash can be increased or decreased depending on the amount, and is not particularly limited, but it is usually 0.
0.01 to 2 parts by weight, particularly 0.01 to 1 part by weight, is preferable from the viewpoint of effectiveness and economy. Moreover, it is also possible to use one or more types together.

Examples of anionic surfactants include dodecylbenzenesulfonate, oleate, alkylbenzenesulfonate, dialkylsulfosuccinate, lignosulfonate, alcohol ethoxysulfate, secondary alkanesulfonate, and α-olefin. There are sulfonic acids, tamol, etc., and commercially available products such as carboxylic acids, sulfuric esters, sulfonic acids, phosphoric esters, and alkylaryl sulfonate products that contain them, or formalin of naphthalene sulfonic acid that may have an alkyl group. A metal shrinkage product or a salt thereof can be used as a dispersant or a wetting agent.

Examples of nonionic surfactants include alkyl polyether alcohols, alkylaryl polyether alcohols, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyalkylene oxide block copolymers. type, jetanolamine type, anhydrosorbitol type, glycoside type.

Commercially available products such as gluconamide-based, glycerin-based, and glycidol-based products can be used as dispersants or particle wetting agents.

Moreover, an antifoaming agent can also be added to suppress foaming. As the antifoaming agent, for example, silicone emulsion is used. Freezing point depressants can also be added to prevent freezing in winter. As the freezing point depressant, for example, a lower alcohol such as ethylene glycol or a polyhydric alcohol is used.

The method for producing the slurry composition of the present invention is not particularly limited, and consists of mixing coal, water, and the dispersant and auxiliary agent used in the present invention in a desired manner.

For example, coal is dry-pulverized in advance and then mixed into an aqueous solution containing a dispersant and auxiliaries; a slurry is made and then the powder and auxiliary agents are added; Any method can be used, such as adding an auxiliary agent and mixing the 5 coals while pulverizing them.

In addition, components (a) and (b) may be added at the same time or
Needless to say, it may be divided and added.

The particle size of the coal (c) is not particularly limited and may be powder or fine particles, but it is preferable that the coal (c) has a 200 mesh pass content of 70% by weight or more.

Effect> In the present invention, it is essential that the slurry composition contains a dispersant and an auxiliary agent made of a specific sulfonated polymer. The dispersant is adsorbed on the surface of the coal particles, and the resulting electrostatic force and the relatively large steric hindrance of the dispersant itself prevent the particles from approaching each other and promote the dispersion of the particles. On the other hand, although the effect of the auxiliary agent is not certain, it is probably to capture the heavy metal ash contained in the coal and to contain any interference with the effect of the dispersant.

A highly concentrated coal-water slurry with good fluidity and excellent long-term stability can be obtained.

<Effects of the Invention> The high-grade coal-water slurry composition of the present invention employs a specific sulfonated polymer as described above as a dispersant,
By using a specific auxiliary agent, the slurry always has high fluidity and excellent long-term stability, regardless of the properties of the coal used. Therefore, when producing slurry.

There is no need to limit the amount of coal in particular, and coal can be supplied from a wide range of sources, which is not only economically advantageous, but also has a great advantage in terms of stable supply of slurry.

<Examples> Hereinafter, the present invention will be described in more detail with reference to Examples. Note that % in the examples is based on weight. In addition, the following abbreviations were used in the examples.

Dicyclopentadiene: DCP ethylidene norbornene: ENBl, 3-butadiene: 1. a-B.

Tetrasodium ethylenediaminetetraacetate: EDTA・4N
Note that the components (a), (b), and (c) of the present invention and their composition ratios are not limited to those described below.

Actual JI Examples 1-30. Comparative Examples 1 to 15 Dry grinding with a ball mill, 200 mesh passes were
Pulverized coal containing ~85% was used for slurry preparation.

To prepare the slurry, add (a) to water [component (d)] in advance.
(b) Put the ingredients into it and put a predetermined amount of pulverized coal [(
Ingredient C)] was first stirred by hand for 3 minutes using a stainless steel spatula, and then stirred at 3000 rpm for 15 minutes using a homomixer (manufactured by Tokushu Kikako ■).

The slurry viscosity was measured at a temperature of 25° C. using a Roto Visco RV-12 rheometer manufactured by Haake. The viscosity at a shear rate of 100 sec'-'' (return trip) was taken as the representative viscosity of the slurry.

The fluidity of the slurry was evaluated by filling the slurry into a rubber cone with a spacing of 24 mm, an upper diameter of 40 m, and a height of 30 nn, and measuring the spread of the slurry when the cone was removed. The evaluation criteria are as follows.

1 sickle Spread of slurry 9 75m+ or more Q 60-75 m Δ 45-60mm It was evaluated by determining the hardness over time. What is the consistency of the slurry? ll! The diameter is 10n
This was done by penetrating a glass rod of 50 m into the slurry. Note that the evaluation criteria are as follows.

1 Starvation-1 ◎: The glass rod penetrates to the bottom of the container under its own weight (approximately 60 g).

○: When the glass rod is pushed by hand, it penetrates to the bottom of the container.

Δ: Even if the glass rod is pushed by hand, it will not penetrate to the bottom of the container.

×: Even if the glass rod is pressed by hand, it does not penetrate at all.

First, evaluate the slurry viscosity, fluidity, and stability.
Shown in Tables 1 and 2.

- An example of a lump ""22" - Dry grinding in a ball mill, 200 metsushipas worth 80
Pulverized coal containing ~85% was used for slurry preparation.

To prepare the slurry, add (a) to water [component (d)] in advance.
Put only the ingredients, and add a predetermined amount of pulverized coal [(C
) ingredients], first knead for 3 minutes with a stainless steel spatula, then use a homo mixer at 3000 rpm,
After stirring for 5 minutes, component (b) was added and further stirring was carried out for 10 minutes at 3000 rpm using a homomixer.

Evaluation of various properties of the slurry was performed according to Example-1. The results are shown in Table 2.

[...136-40 (a) A slurry was prepared according to the procedure of Example 31 except that the order of addition of components (b) was reversed. Evaluation of various properties of the slurry was conducted in accordance with Example-1. The results are shown in Table 3.

Claims (6)

[Claims] (1) (a) Number of carbon atoms containing two double bonds in the molecule: 9
Sulfonated products of ~12 norbornene derivatives, sulfonated products of cyclohexane derivatives with 8 to 12 carbon atoms containing 2 double bonds in the molecule, and fats with 4 to 7 carbon atoms containing 2 double bonds in the molecule (b) a polymer obtained by polymerizing at least one sulfonated product selected from the group of sulfonated group dienes; (c) coal, and (d) water, containing 0.01 to 10 parts by weight of (a) and 0.001 to 2 parts by weight of (b) per 100 parts by weight of (c). A coal-water slurry composition characterized in that: (2) As component (b) described in claim 1,
The coal-water slurry composition according to claim 1, which uses a hydroxycarboxylic acid and/or a salt thereof. (3) As component (b) described in claim 1,
The coal-water slurry composition according to claim 1, which uses gluconic acid and/or a salt thereof. (4) The above component (a) is 0.05 to 2 parts by weight per 100 parts by weight of coal (c), and the component (b) is 0.05 to 2 parts by weight per 100 parts by weight of coal (c).
The coal-water slurry composition according to claims 2 to 4, which is used in an amount of 0.01 to 1 part by weight. (5) The coal-water slurry composition according to claim 1, wherein the organic chelating agent is an aminocarboxylic acid and/or a salt thereof. (6) The coal-water slurry composition according to claim 1, wherein the coal (c) is a powder having a content passing through 200 mesh of 70% by weight or more.