JPH0252032A - Dispersant and solid fuel slurry composition - Google Patents

Abstract

PURPOSE:To obtain a dispersant for slurrying solid fuel by increasing the surface tension of an aqueous solution by a sulfonated aliphatic diene (co)polymer with uniform sulfonic acid content prepared by a specific method. CONSTITUTION:A dispersant for slurrying solid fuel such as coal or petroleum coke is prepared by sulfonating a polymer, which is obtained by polymerizing an aliphatic diene such as 1,3-butadiene or isoprene, by a complex consisting of anhydrous sulfuric acid and an electron donating compound such as dioxane. This dispersant is based on a sulfonated aliphatic diene (co)polymer wherein sulfonic acid content is 4-5.4mumol/g and the surface tension of an aqueous solution is 50 dyne/cm or more. A solid fuel slurry composition using this dispersant has good slurry dispersibility and shows standing stability, mechanical stability and thermal stability.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a specific dispersant and a solid fuel slurry composition containing the same.

[Conventional technology]

Traditionally, the energy structure has been based on petroleum, but in recent years, due to the depletion of petroleum resources, solid fuels such as coal, petroleum coke, and pinch have been rediscovered, and various ways of using them are being considered.

However, unlike liquid fuels such as petroleum, these solid fuels are solid and therefore difficult to transport by ordinary pipelines, tank trucks, and the like.

For this reason, conventionally, as a means of transporting these solid fuels,
Methods include pulverizing solid fuel and mixing it with water to make a water slurry composition, or adding a surfactant to such a water slurry composition to improve the dispersibility and stability of solid fuel in water. It has started to be proposed.

[Problem to be solved by the invention]

However, in the former water slurry composition, when the concentration of solid fuel is increased, the viscosity of the composition increases and fluidity deteriorates, while when the concentration is decreased, stabilization of the slurry is hindered and combustion efficiency is deteriorated. It has problems such as:

Furthermore, even in the case of water slurry compositions containing the latter surfactant, the dispersibility and stability over time of the slurry have not yet reached a fully satisfactory level.

The present invention was made against the background of these conventional technical problems, and it is the discovery of a specific new dispersant, which can achieve higher solid fuel concentration and lower dispersant addition than conventional dispersants. It is an object of the present invention to provide a solid fuel slurry composition that can provide high fluidity to the slurry, and can maintain high fluidity even after being left for a long time.

[Means to solve the problem]

The present invention is obtained by sulfonating an aliphatic diene (co)polymer using a complex consisting of sulfuric anhydride and an electron-donating compound, and has a sulfonic acid content of 4 to 5.4 mmol/g.
The present invention provides a dispersant containing as a main component a sulfonated aliphatic diene (co)polymer having a surface tension of 50 dynes/c11 or more in aqueous solution.

The present invention also provides a solid fuel slurry composition containing the above-mentioned (a) dispersant, [b) solid fuel powder, and (c) water as main components.

In the present invention, the aliphatic diene that is the raw material for the dispersant [component (a)] is a carbon compound containing two double bonds in the molecule.
4 to 7 hydrocarbons, and examples of the aliphatic diene include 1,3-butadiene, 1,2-butadiene,
1,2-pentadiene, 13-pentadiene, 2,3-
Pentadiene, isoprene, l,2-hexadiene, ■
, 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-hebutadiene, ■, 4-heptadiene, 1.5
-Hebutadiene, 1,6-hebutadiene, 2,3-hebutadiene, 2,5-hebutadiene, 3,4-heptadiene, 3,5-heptadiene, etc., as well as various branched dienes with 4 to 7 carbon atoms 1.3-, preferably 1.3-
They are butadiene, isoprene, and 1,3-pentadiene.

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

Further, in the present invention, other copolymerizable monomers (hereinafter referred to as "other monomers") can also be used in combination with the aliphatic diene.

Other monomers include aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate. , 2-hydroxyethyl acrylate, 2-
Alkyl esters of acrylic acid or methacrylic acid such as hydroxyethyl methacrylate; acrylic acid,
Mono- or dicarboxylic acids or dicarboxylic acid anhydrides such as methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid; vinyl cyanide compounds such as acrylonitrile, methacrylaterile; vinyl chloride, vinylidene chloride, vinyl methyl ethyl ketone, vinyl methyl ether, Compounds containing unsaturated groups such as vinyl acetate, vinyl formate, allyl acetate, methalylacetate, acrylamide, methacrylamide, N-methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, acrolein, allyl alcohol; ethylene oxide, propylene oxide, tetrahydrofuran, Examples include cyclic compounds such as styrene oxide and butylene oxide.

These other monomers can be used alone or in combination of two or more.

When these other monomers are used together, the amount of these monomers used is 70% or less, preferably 1 to 5% of the total monomers.
It is about 0% by weight, more preferably about 2 to 30% by weight.

Aliphatic diene (co) used in the (81 dispersant) of the present invention
The polymer refers to a polymer obtained by polymerizing at least one of the aliphatic dienes mentioned above, or a polymer obtained by copolymerizing the aliphatic diene and other monomers when other monomers are used together. It is a random copolymer obtained by polymerization.

The method for producing such a (co)polymer is as follows.

For example, the aliphatic diene (and other monomers) can be combined with a radical polymerization initiator such as hydrogen peroxide, benzoyl peroxide, or azobisisobutyronitrile; or an anion such as n-butyllithium, sodium naphthalene, or sodium metal. In the presence of a polymerization initiator, etc., the reaction temperature is usually -
100-150°C, preferably 0-130°C, 0.1
A (co)polymer can be produced by carrying out a polymerization reaction for ~20 hours.

In the above (co)polymerization reaction, a polymerization reaction solvent can be used to smoothly carry out the reaction, and the polymerization reaction solvent may be a polar solvent such as water, or a carbonized solvent as long as it does not interfere with the (co)polymerization reaction. Any hydrogens, halogenated hydrocarbons, etc. can be used.

The molecular weight of the aliphatic diene (co)polymer thus obtained can be changed as appropriate depending on the reaction conditions, especially the type and amount of the polymerization initiator, the type and amount of the solvent, or the reaction temperature and reaction time. can.

For example, when this aliphatic diene (co)polymer is used as a raw material for a dispersant for solid fuel, the characteristics cannot be unambiguously determined because they vary depending on the type of solid fuel, particle size, etc., but usually several Average molecular weight is 300-500,0
00, preferably 1.000 to 200,000.

The dispersant (8) used in the present invention is obtained by sulfonating the aliphatic diene (co)polymer using a complex consisting of sulfuric anhydride and an electron-donating compound.

Here, the amount of sulfuric anhydride used is usually 0 to 1 mole of aliphatic diene unit in the aliphatic diene (co)M combination.
．． 6 to 1.2 mol, preferably 0.7 to 1.1 mol; less than 0.6 mol reduces the dispersibility and mechanical stability of the composition of the present invention, while more than 1.2 mol and the dispersibility of the composition decreases.

Examples of electron-donating compounds include dioxane, trialkyl phosphoric acid, pyridine, N,N-dimethylformamide, dibutyl ether, tetrahydrofuran, diethyl ether, triethylamine, trimethylamine, tributylamine, dimethyl sulfide, diethyl sulfide, acetonitrile, and ethyl nitrile. Examples include compounds that form a complex with sulfuric anhydride, such as propylnitrile, and dioxane is particularly preferred.

In the production of this complex, the amount of the electron donating compound used is usually 0.00 to 1 mole of sulfuric anhydride. 5 moles or more,
The amount is preferably 1 mole or more, more preferably 2 to 10 moles, and less than 0.5 mole is undesirable because side reactions may occur during sulfonation and carbonization of the aliphatic diene (co)polymer may occur.

In addition, the reaction temperature during this complex formation is usually 40°C or lower, preferably 30°C or lower, and more preferably 10 to 2
The temperature is 5°C, and if it exceeds 40°C, the rate of complex formation becomes extremely high, side reactions are likely to occur, and the electron donating compound is carbonized, which is not preferable.

Note that during sulfonation, it is desirable to add this complex to the aliphatic diene (co)polymer, or to add both at the same time. During sulfonation, the addition of an aliphatic diene (co)polymer into the complex reduces the surface tension of the resulting sulfonate, resulting in bubbles in the slurry composition, which not only causes cavitation problems. , dispersibility and mechanical stability deteriorate.

In order to uniformly and smoothly proceed the sulfonation reaction of the aliphatic diene (co)polymer, an appropriate solvent can be used.

Solvents that can be advantageously used include, for example, n-pentane,
Saturates with 5 to 10 carbon atoms and no tertiary carbon, such as n-hexane, n-hebutane, n-octane, n-nonane, n-decane, cyclobencune, cyclohexane, cyclohebutane, cyclooctane, cyclononane, and cyclodecane. Hydrocarbons include halogenated hydrocarbons such as chloroform, carbon tetrachloride, and dichloroethane; and the aforementioned electron-donating compounds.

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

The reaction temperature for sulfonation is usually -60 to 80°C, preferably -20 to 40°C; below -60°C, the sulfonation reaction rate slows down and the sulfonation efficiency deteriorates; Exceeding this is undesirable as carbide formation occurs.

Moreover, sulfonation can be carried out either under normal pressure or under increased pressure.

The cationic species of the resulting sulfonated product is not particularly limited, but in order to make it water-soluble, basic compounds such as hydrogen atoms, alkali metals, alkaline earth metals, ammonium, and amines are preferred.

These basic compounds include metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, zinc hydroxide, and cadmium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide, and sodium hydroxide. -t-butoxide, potassium-t-
Alkali metal alkoxides such as butoxide; methyllithium, ethyllithium, n-butyllithium, 313
G-butyllithium, amyllithium, propyl sodium, methylmagnesium chloride, ethylmagnesium bromide, propylmagnesium iodide,
Organometallic compounds such as diethylmagnesium, diethylzinc, triethylaluminum, and triisobutylaluminum; amines such as aqueous ammonia, trimethylamine, triethylamine, tripropylamine, pyridine, and piperazine; metal compounds such as sodium, lithium, potassium, calcium, and zinc Among these basic compounds, alkali metal hydroxides, particularly sodium hydroxide, are preferred. These basic compounds can be used alone or in combination of two or more.

The amount of the basic compound used is usually 0.1 to 1 mole of sulfuric anhydride, which is the sulfonating agent used during sulfonation.
3 mol, preferably 0.5 to 2 mol; less than 0.1 mol results in poor water solubility of the product, leading to a decrease in dispersion performance when used as a dispersant, whereas more than 3 mol This is not preferable because a large amount of unreacted basic compounds remain and the purity decreases.

The degree of neutralization of the sulfonic groups at this time may be appropriately selected within a range that makes the sulfonated product or its salt water-soluble or water-dispersible, and furthermore, the degree of neutralization of the sulfonic groups may be appropriately selected within a range that makes the sulfonated product or its salt water-soluble or water-dispersible. It's okay.

The structure of the sulfonated compound (salt) used in the present invention can be confirmed from the absorption of sulfonic groups by infrared absorption spectrum, and the composition ratio can be determined by acid/alkali titration of potential difference, conductivity, etc. .

Furthermore, its structure can be confirmed by nuclear magnetic resonance spectroscopy.

The dispersant (a) used in the present invention is a sulfonated product of the above aliphatic diene (co)polymer or a salt thereof (
The sulfonic acid content of this sulfonated product (salt) is 4 to 5.4 mmol/g, preferably 4.4 to 5.2 mmol/g, and It is necessary that the surface tension be at least 50 dynes/cffi, preferably at least 55 dynes/a.

If the sulfonic acid content of the sulfonated product (salt) is less than 4 mmol/g, the dispersibility and mechanical stability of the resulting composition will decrease, and the required amount of dispersant (81) will increase, resulting in poor economic efficiency. If it exceeds 5.4 mmol/g, the dispersibility and fluidity of the composition will deteriorate, which is not preferable.

In addition, the surface tension of the sulfonate (salt) is 50 dyne/c.
If the amount is less than m, the dispersibility of the resulting composition is reduced, a large number of bubbles are generated in the composition, and undesirable phenomena such as cavitation occur when the composition is transferred with a slurry pump.

The dispersant used in the present invention may be the sulfonated product (salt) used alone, but even better effects can be obtained by using it in combination with other water-soluble polymers.

Other water-soluble polymers include: (a) Polymers containing naphthalenesulfonic acid (salt) structural units, such as aldehyde condensates of naphthalenesulfonic acid (salt), polyvinylnaphthalenesulfonic acid (salt), etc. (b) Lignin Polymers containing sulfonic acid (salt) structural units and derivatives thereof; (c) Polymers containing styrene sulfonic acid (salt) structural units, such as polystyrene sulfone #I (salt), styrene/
Styrene sulfonic acid (salt) copolymer; polymer containing (d)norbornenesulfonic acid (salt) structural unit, e.g. 5
- (Co)polymers of sulfonated norbornene derivatives such as propenyl-norbornene-2, dicyclopentadiene, and 5-ethylidene-norbornene-2; (v) Polymers containing carboxylic acid (salt) structural units, such as ( (co)polymers such as meth)acrylic acid, maleic acid, fumaric acid, and phthalic acid; (f)polymers containing polyether structural units, such as (co)polymers such as ethylene oxide, butylene oxide, and styrene oxide; Examples include derivatives of polyalkylene glycol mono(meth)acrylate. These water-soluble polymers can be used alone or in combination of two or more.

The ratio of the sulfonated product (salt) used in the present invention and the water-soluble polymer is usually 15 to 95% by weight.
% by weight, preferably 25-75% by weight, the latter being 85-5% by weight
If the amount of the sulfonated compound (salt) is less than 15% by weight, the dispersibility, static stability, thermal stability, and mechanical stability of the resulting composition may deteriorate. Any one or more of them decreases, which is not preferable.

Sulfonated compound (salt) used in (8) dispersant of the present invention
When prepared as an aqueous solution, it can be used as a dispersant as it is, but if necessary, a solid water-soluble sulfonated product (salt) can also be obtained by separating and drying these salts from the aqueous solution.

Next, the solid fuels used in the present invention are coal, petroleum coke, pi-sochi, and charcoal.

The coal may be lignite, sub-bituminous coal, bituminous coal, anthracite, etc., or may be coal obtained by cleaning these coals without any particular limitation.

Petroleum coke is residual coke produced by distilling asphalt, pitch, etc., which are obtained as heavy residues from distillation during petroleum refining, at higher temperatures to distill cracked oil, and is generally made from coal containing non-materials. It is extremely difficult to get wet with water compared to .

Pitch is a heavy residue obtained by distilling petroleum distillation and tar obtained by coal carbonization, leaving an oil content, and its softening point is preferably 50 to 180 ° C.
If the temperature is lower than 50°C, pulverization is difficult. Compared to coal, pitch contains almost no ash and moisture and can be made into a slurry fuel with a high calorific value.

The particle size of these solid fuels may be any particle size as long as it is powder, but since the pulverized coal currently burned in thermal power plants has a 200 mesh bath content of 70% by weight or more, this particle size is suitable. is a rough guideline.

However, the dispersant used in the present invention is not affected by particle size or type of solid fuel, and exhibits excellent effects on any solid fuel powder.

The dispersant of the present invention can be used in combination with one or more kinds of surfactants, additives, etc. described later as necessary, but is not particularly limited.
It is added to a solid fuel slurry having a solid fuel concentration of 50 to 85% by weight, preferably 60 to 80% by weight based on the total composition.

As the amount of the dispersant added increases, the viscosity of the slurry decreases, so the amount added can be selected depending on the desired viscosity, and is usually 0.01 to 10% based on the total amount of the slurry composition.
It may be 0.0% by weight, but from the viewpoint of workability and economy.
5 to 2% by weight is preferred.

Surfactants optionally used in the slurry composition of the present invention include dodecylbenzenesulfonate, oleate, alkylbenzenesulfonate, dialkylsulfosuccinate, lignosulfonate, alcohol ethoxysulfate, secondary alkanesulfonate,
There are α-olefin sulfonic acids, tamol, etc., and commercially available products containing them such as carboxylic acid, sulfate ester, sulfonic acid, phosphoric ester, and alkyl sulfonate are used as dispersants or wetting agents. be able to.

Examples of additives include chelating agents for trapping polyvalent metals contained in ash in solid fuel, potassium tetrapolyphosphate, sodium citrate, sodium gluconate, sodium polyacrylate, and polycarboxylic acids.

Moreover, an antifoaming agent can also be added to suppress foaming. Examples of antifoaming agents include silica silicone emulsions, metal soap emulsions, amide emulsions, ester emulsions, and polyether emulsions, and among these emulsions, silica silicone emulsions are most preferred.

Furthermore, organic and inorganic stabilizers are effective; organic stabilizers include cellulose-based semi-synthetic thickeners and xanthan gum, and inorganic stabilizers include bentonite.

Furthermore, freezing point depressants can 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 solid fuel, water, and the dispersant used in the present invention in a desired manner.

For example, solid fuel is dry-pulverized in advance and then mixed into an aqueous solution containing a dispersant, a slurry is made and then a dispersant is added, and solid fuel is ground in a mill.
Any method can be used, such as adding water and a dispersant and mixing the fuel while pulverizing it.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, in the examples, % is based on weight.

In addition, various measurements in the Examples were performed in accordance with the following.

To determine the sulfonic acid content, prepare a 20% aqueous solution of each dispersant,
Dialysis membrane (manufactured by Hanui Chemicals, Ce1luloseDio)
lyzer Tubing-VT351) to remove low-molecular substances and purify the sample.
After ion-exchanging with R-118(H) to completely convert it into an acid form, the sulfonic acid content was determined by potentiometric titration.

The surface tension was measured using a 4% aqueous solution of each dispersant using a surface tension meter.

The number average molecular weight was measured by gel permeation chromatography (GPC) using polystyrene or sodium polystyrene sulfonate as a standard sample.

Dispersibility was determined by measuring the viscosity of the coal slurry at 25°C.

The standing stability was evaluated by allowing the coal slurry to stand for 30 days, measuring the viscosity after standing, and comparing it with the initial viscosity. In addition, viscosity after 30 days/initial viscosity=P, and when P was 2 or less, it was evaluated as ○, and when P exceeded 2, it was evaluated as ×.

Mechanical stability was evaluated by stirring the coal slurry for 60 minutes using a homomixer at 3.00 rpm, measuring the viscosity after stirring, and comparing it with the initial viscosity. Note that viscosity after 60 minutes/initial viscosity = Q, and cases where Q exceeds 0.2 from 2 or less were evaluated as ×.

Thermal stability was evaluated by standing the coal slurry at 80° C. for 10 minutes, measuring the viscosity after the standing, and comparing it with the initial viscosity. Note that viscosity at 80° C./initial viscosity = R, and when R was 0.8 or less, it was evaluated as Olo, and when R was over 8, it was evaluated as ×.

Low additive properties were evaluated by comparing the amount of dispersant with the viscosity of a coal slurry at 0.3% of coal and the viscosity of a coal slurry at 0.5% of coal. Note that the viscosity of the coal slurry at 0.3% and the viscosity of the coal slurry at 10.5% = S, and S is 1.
A value of 3 or less was evaluated as O, and a value of over 1.3 was evaluated as ×.

Reference Example 1 ■ 35.0 g of isoprene, 0.44 g of n-butyl lithium, and 200 g of cyclohexane were placed in a pressure-resistant reaction vessel, and after polymerizing at 60 to 90°C for 4 hours, 1 g of isopropyl alcohol (IPA) was added to stop the polymerization. did.

Next, after distilling off the solvent and unreacted monomers under reduced pressure,
1. Diluted with 50 g of 2-dichloroethane.

■Next, in a separate container, add 150% N,N-dimethylformamide.
45.3 g of sulfuric anhydride was added to the mixture while maintaining the inner bath at 25° C., and the mixture was stirred for 2 hours to obtain a sulfuric anhydride-N,N-dimethylformamide complex.

(2) The complex obtained in (2) above was added to the polymer solution obtained in (2) above over a period of 1 hour while maintaining the inner bath at 10°C. After the addition, stirring was continued for 2 hours, and then 25.0 g of sodium hydroxide and 150 g of water were added, followed by stirring for 1 hour.

After stirring, water and the solvent were distilled off under reduced pressure to obtain a compound salt as a yellow powder.

This product is called Polymer 1.

Reference Example 2 (1) A pressure-resistant reaction vessel was charged with 35.0 g of isoprene, 0.44 g of n-butyllithium, and 200 g of cyclohexane, and after polymerization at 60° C. for 2 hours, 1 g of isopropyl alcohol (IPA) was added to stop the polymerization.

Next, after distilling off the solvent and unreacted monomers under reduced pressure,
Diluted with 50 g of 1,2-dichloroethane.

■ Next, add 32 sulfuric anhydride to 100 g of dioxane in a separate container.
．． 9 g was added while keeping the internal temperature at 25° C., and stirred for 2 hours to obtain a sulfuric anhydride-dioxane complex.

(2) The complex obtained in (2) above was added to the polymer solution obtained in (2) above over a period of 2 hours while maintaining the internal temperature at 1.degree. After the addition, stirring was continued for 2 hours, and then 18.0 g of sodium hydroxide and 150 g of water were added, followed by stirring at 80° C. for 1 hour. After stirring, water and the solvent were distilled off under reduced pressure to obtain a yellow powder sulfonate salt product.

This product is called Polymer 2.

In order to investigate the sulfonic acid distribution of the sulfonated polymer of this reference example, the sulfonic acid content was measured during the reaction, and the results are shown in FIG.

As is clear from FIG. 1, in this reference example, the sulfonic acid content increases proportionally as the sulfonation reaction time progresses, and it can be inferred that the sulfonated product has a homogeneous composition.

Reference Example 3 (1) A pressure-resistant reaction vessel was charged with 35.0 g of isoprene, 0.12 g of n-butyllithium, and 200 g of cyclohexane, and after polymerization at 60° C. for 2 hours, 1 g of isopropyl alcohol (IPA) was added to stop the polymerization.

Next, after distilling off the solvent and unreacted monomers under reduced pressure,
Diluted with 50 g of dioxane.

■ Next, add 32 sulfuric anhydride to 100 g of dioxane in a separate container.
．． 9 g was added while keeping the internal temperature at 25° C., and stirred for 2 hours to obtain a sulfuric anhydride-dioxane complex.

(2) The complex obtained in (2) above was added to the polymer solution obtained in (2) above over 1 hour while maintaining the internal temperature at 25°C. After the addition, stirring was continued for 1 hour, and then 15.0 g of sodium hydroxide and 150 g of water were added, followed by stirring at 80° C. for 1 hour. After stirring, water and the solvent were distilled off under reduced pressure to obtain a yellow powder sulfonate salt product.

Reference Example 4 Example 1 was repeated except that 35.0 g of isoprene was changed to 28.0 g of 13-butadiene, the amount of sulfuric anhydride was changed to 32.9 g, and the amount of sodium hydroxide was changed to 16.5 g. The product was obtained in the same manner.

Reference Example 5 In Reference Example 2, 35.0 g of isoprene was changed to 24.7 g of 1°3-pentadiene, and the amount of n-butyllithium was 0.
．． A product was obtained in the same manner as in Example 1, except that the amount of sulfuric anhydride was changed to 24.7 g, and the amount of sodium hydroxide was changed to 12.4 g.

Reference Example 6 In Reference Example 1, 35.0 g of isoprene was added to 28.0 g of 13-butadiene and 3 g of methyl methacrylate,
Also, the amount of n-butyllithium was changed to 0.12g, the amount of sulfuric anhydride was changed to 24.7g, and the amount of sodium hydroxide was changed to 1.
A product was obtained in the same manner as in Example 1 except that the amount was changed to 2.4 g.

Reference Example 7 In Reference Example 2, 35.0 g of isoprene was changed to 17.5 g of 1°3-pentadiene, the amount of n-butyllithium was changed to 0.12 g, the amount of sulfuric anhydride was changed to 41.2 g, and the amount of sodium hydroxide was changed to 0.12 g. A product was obtained in the same manner as in Reference Example 1 except that the amount was changed to 20.6 g.

Reference Example 8 In the reference example process, 7 g of azobisisobutyronitrile was used instead of n-butyllithium, the polymerization time was changed to 8 hours, the amount of sulfuric anhydride was changed to 16.5 g, and the amount of sodium hydroxide was changed to 16.5 g. A product was obtained in the same manner as in Reference Example 1, except that the amount was changed to 8.3 g.

Reference Example 9 On the day of Reference Example, a product was obtained in the same manner as Reference Example 8, except that 13-butadiene was used instead of isoprene.

Reference Examples 10 to 15 As shown in Table 1, the polymer 1 or polymer 2, formalin condensate of sodium naphthalene sulfonate, sodium lignin sulfonate, sodium polystyrene sulfonate, sodium polyacrylate, ethylene oxide/propylene oxide, etc. A polymer or a blend of sulfonated dicyclopentadiene with a polymer was used as a dispersant.

Reference Example 16 The same procedure as in Reference Example 2 was carried out, except that the method was changed to adding the polymer solution obtained in step (2) above into the anhydrous sulfuric dioxane complex obtained in step (1) over a period of 2 hours. The product was obtained.

In order to investigate the sulfonic acid distribution of the sulfonated polymer of this reference example, the sulfonic acid content was measured during the reaction, and the results are shown in FIG.

As is clear from Figure 1, this reference example shows a high sulfonic acid content at the beginning of the sulfonation reaction, which is because the obtained sulfonated product is a mixture of high and low sulfonic acid contents. It shows that it is.

Reference Example 17 A product was obtained in the same manner as in Reference Example 2, except that the amount of sulfuric anhydride was changed to 16.5 g and the amount of sodium hydroxide was changed to 8.2 g.

Reference Example 18 Same as Reference Example 2 except that the amount of sulfuric anhydride was changed to 53.5 g and the amount of sodium hydroxide was changed to 26.8 g.
The product was obtained in the same manner.

Reference Example 19 In a stainless steel autoclave with an internal volume of 301 mm equipped with a stirring device and a thermometer, 1,000 ml of 1,3-pentadiene was added.
g, sodium bisulfite 1,530 g, potassium nitrate 62.5 g, methyl alcohol 37! , and distilled water 1
, 500g, and the internal pressure in the autoclave was 1 at room temperature.
．． After supplying nitrogen gas to 0 kg/cd·G, the valve was sealed and the mixture was reacted at 110° C. for 5 hours while mixing under strong stirring.

After that, it was left to cool to room temperature, and most of the methyl alcohol was removed by distillation, then distilled water and petroleum ether were added and thoroughly mixed, and the separated petroleum ether stone and precipitate were removed to form an aqueous layer. Concentrate and evaporate to dryness. This was dissolved in glacial acetic acid, and the acetic acid insoluble portion consisting of inorganic salts was separated using a centrifuge. By concentrating the obtained acetic acid soluble content, 1,200 g of a white solid was obtained. This is referred to as sulfonated compound A.

Next, 1.0% of the sulfonated compound A was placed in a glass-lined autoclave with an internal volume of 5N equipped with a stirring device.
1.0 kg of sulfuric acid and 0.45 kg of water.
A polymerization reaction was carried out at 120° C. for 12 hours.

After the reaction was completed, sulfuric acid was removed by writhing with calcium carbonate, and the solid content obtained was 0.9 kg.

The number average molecular weight of this product was 23,000. Further, the surface tension of a 4% aqueous solution of this product was as high as 63.8 dynes/mouth.

24 g of the obtained polymer was dissolved in 1,000 g of water,
Strongly acidic cation exchange resin 1,0 which has been converted into acid form
After standing for day and night, the filtrate from which the resin was removed by filtration was dried.

When we conducted an elemental analysis of this material, we found that it contained 39.0% carbon.
, hydrogen 6.6%, sulfur 22.1%, oxygen 32.3%, which is the theoretical value of this polymer, carbon 40.0%, hydrogen 6%.
．． 7%, sulfur 21.3%, and oxygen 32.0%.

Next, when this product was subjected to neutralization titration with sodium hydroxide, it was neutralized with an equivalent amount of sodium hydroxide. These results indicate that in the polymer after the cation exchange treatment, the sulfone groups were converted into sodium salts after being neutralized. The sulfonic acid content was 5.8 mmol/g. Furthermore, the surface tension of a 4% aqueous solution of this polymer salt is 64.2 dynes/c.
It was II+.

Reference Example 20 Polymer solution obtained in Reference Example 2 (■) and 100 g of dioxane
and 32.9 g of sulfuric anhydride and 1.2-
Consisting of 100g of dichloroethane? Each method was maintained at an internal temperature of 25°C and added over 2 hours.

After the addition, stirring was continued for 2 hours, and then 1 part of sodium hydroxide was added.
8.0 g and 150 g of water were added, and the mixture was stirred at 80° C. for 1 hour. After stirring, water and solvent were removed under reduced pressure. The product using a complex such as Reference Example 1 was pale yellow, but the product of this Reference Example, which did not use a complex, was a blackish brown water-soluble polymer, and a tar-like product was not produced. Ta.

Table 2 shows the sulfonic acid content, surface tension, and number average molecular weight of the dispersants obtained in Reference Examples 1 to 9 and Reference Examples 15 to 20.

Table 2 Examples 1 to 15, Comparative Examples 1 to 5 The coal was produced in Australia and was 8
0%, ash content of 6.5%, and sulfur content of 1.6%.

Add the dispersant listed in Table 3 (coal 0) to the water in advance.
．． 5%), a predetermined amount of coal particles were gradually added thereto, and the mixture was stirred for 15 minutes at 3.00 Orpm using a homomixer to prepare a coal slurry with a concentration of 70%.

The coal slurry thus obtained was also evaluated. The results are shown in Table 3.

As is clear from Table 3, the slurry composition obtained according to the present invention has a low viscosity and is excellent in static stability, mechanical stability, thermal stability, and low additive property.

On the other hand, the coal slurry prepared by adding the aliphatic diene polymer of Comparative Example 1 to the sulfuric anhydride-dioxane complex and using the sulfonated product with low surface tension as a dispersant has low static stability and thermal stability. The slurry was poor in low additivity, and especially in the low additivity, the dispersion state of the slurry was so poor that the viscosity could not be measured.

Furthermore, Comparative Example 2 with a low sulfonic acid content has the drawbacks of poor dispersion stability and vigorous foaming, making it difficult to produce a slurry.

Furthermore, in Comparative Example 3, in which the sulfonic acid content was added in a large amount outside the range of the present invention, it was difficult to prepare a slurry and it could not be evaluated as a slurry.

Furthermore, in Comparative Example 4, a commercially available condensate of sodium naphthalene sulfonate and formalin was used as a dispersant, and the slurry had a high viscosity and had poor static stability, mechanical stability, and low additive properties.

Furthermore, in Comparative Example 5, a commercially available ethyl oxide/propylene oxide copolymer was used as a dispersant, and although the slurry viscosity was low, the mechanical stability, thermal stability,
Low additive properties are poor.

Examples 16-18, Comparative Examples 6-8 Contains 70% of 200 mesh bath and 0.65% ash
, petroleum coke containing 0.30% sulfur was used.

3. Pour the dispersant listed in Table 3 into water, gradually add a predetermined amount of petroleum coke into the water, and mix with a homomixer. A petroleum coke water slurry was prepared by stirring at OOOrpm for 15 minutes.

The petroleum coke concentration was 70%, and the amount of dispersant added was constant at 0.5% relative to petroleum coke.

The coal slurry thus obtained was evaluated. The results are shown in Table 3.

As is clear from Table 3, the slurry composition obtained according to the present invention has a low viscosity and is excellent in static stability, mechanical stability, thermal stability, and low additive property.

On the other hand, in Comparative Examples 6 and 7, the surface tension of the dispersant was 5
less than 0 dyne/cI1, the resulting slurry composition has a high viscosity, and is poor in any of the various slurry stability;
And low additive properties are poor.

In Comparative Example 8, the sulfonic acid content of the dispersant was 5.4.
Since the amount exceeds mmol/g, the slurry cannot be fluidized.

Comparative Example 9 Using the polymer salt obtained in Reference Example 19 as a dispersant, it was added at a ratio of 0.5% to coal, and a coal slurry was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3.

Comparative Example 9 has excellent dispersibility and static stability, but is inferior in mechanical stability, thermal stability, and low additivity, especially when the dispersant is 0.3% (relative to coal). It showed no fluidity at all.

Comparative Example 10 A coal slurry was prepared and evaluated in the same manner as Comparative Example 9 except that the polymer salt obtained in Reference Example 20 was used. The results are shown in Table 3.

It can be seen that Comparative Example 10 has excellent thermal stability, but is inferior in dispersibility, static stability, reinforcing stability, and low additive property.

It can be seen from Table 3 that the petroleum coke water slurry composition of the present invention is superior.

〔Effect of the invention〕

The dispersant of the present invention is mainly composed of a sulfonated aliphatic diene (co)polymer obtained by a specific production method, has a uniform sulfonic acid content, has a high surface tension of an aqueous solution, The solid fuel slurry composition using this dispersant has the following advantages compared to the composition obtained by conventional technology:
It has good slurry dispersibility and exhibits excellent dispersibility when added in small amounts, as well as static stability, mechanical stability, and thermal stability.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the relationship between the sulfonation reaction time of a sulfonated product and the sulfonic acid content. Patent Applicant Japan Synthetic Rubber Co., Ltd. Agent Patent Attorney Shige Takashi Shirai Reaction Team (Minutes)

Claims (3)

[Claims] (1) Obtained by sulfonating an aliphatic diene (co)polymer using a complex consisting of sulfuric anhydride and an electron-donating compound, with a sulfonic acid content of 4 to 5.4 mmol/g, and on the surface of an aqueous solution. A dispersant whose main component is a sulfonated aliphatic diene (co)polymer having a tension of 50 dynes/cm or more. (2) A solid fuel slurry composition containing (a) the dispersant according to claim 1, (b) solid fuel powder, and (c) water as main components. (3) (a) The dispersant contains 15 to 95% by weight of the aliphatic diene (co)polymer sulfonate and the following (a) to (f).
The solid fuel slurry composition according to claim 1, comprising 85 to 5% by weight of at least one water-soluble polymer selected from the following. (b) Polymers containing naphthalenesulfonic acid (salt) structural units; (b) Polymers containing ligninsulfonic acid (salt) structural units; (c) Polymers containing styrenesulfonic acid (salt) structural units; ) Polymers containing norbornenesulfonic acid (salt) structural units, (e) Polymers containing carboxylic acid (salt) structural units, (f)
A polymer containing a polyether structure.