JPH07242885A - Solid fuel slurry composition - Google Patents

Abstract

PURPOSE:To obtain the subject highly economical composition maintaining its high concentration and high fluidity for a long period, comprising a sulfonated product of aliphatic diene (co)polymer, lignosulfonic acid (salt), clay minerals, solid fuel and water. CONSTITUTION:This solid fuel slurry composition comprises (A) a sulfonated product of aliphatic diene (co)polymer (B) a lignosulfonic acid (salt), (C) clay minerals (e.g. montmorillonite), (D) a solid fuel (e.g. coal), and (E) water, where the component A is prepared by the following processes: a pressure reaction vessel is charged with an aliphatic diene compound (e.g. isoprene) followed by addition of n-butyllithium ad cyclohexane and then conducting a polymerization at 60-90 deg.C for 4hr; subsequently adding isopropyl alcohol to the reactional system to terminate the polymerization followed by removing the solvent and unreacted monomer and adding 1,2-dichloroethane to the system and then adding anhydrous sulfuric acid-dioxane complex to carry out a sulfonation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid fuel slurry composition containing specific additives.

[0002]

2. Description of the Related Art Conventionally, an energy structure mainly composed of petroleum has been taken, but in recent years, solid fuels such as coal, petroleum coke, and pitch have been re-recognized due to the exhaustion of petroleum resources, and various uses thereof have been studied. Has been done. However,
Since these solid fuels are solid unlike liquid fuels such as petroleum, it is difficult to transport them by ordinary pipelines or tank trucks. Therefore, conventionally, as a means for transporting these solid fuels, a method of pulverizing the solid fuel and mixing it with water to prepare an aqueous slurry composition, or adding a surfactant to such an aqueous slurry composition to form a solid fuel A means for improving the dispersibility of water in water and stability has been proposed.

[0003]

However, in the former water slurry composition, when the concentration of the solid fuel is increased, the viscosity of the composition is increased and the fluidity is deteriorated, while when the concentration is decreased, the slurry is stabilized. In addition to being hindered, there are problems such as deterioration of combustion efficiency. Further, even in the latter case of a water slurry composition containing a surfactant, the dispersibility and the temporal stability of the slurry have not yet reached a sufficiently satisfactory range. The present invention has been made against the background of these conventional technical problems, and provides a solid fuel slurry composition excellent in economical efficiency, which maintains high concentration and high fluidity of solid fuel for a long period of time as compared with the prior art. The purpose is to do.

[0004]

The present invention provides (A) a sulfonated product of an aliphatic diene-based (co) polymer, (B) ligninsulfonic acid (salt), (C) clay minerals, (D) solid A solid fuel slurry composition comprising a fuel and (E) water as a main component is provided.

In the present invention, the sulfonated product of the aliphatic diene (co) polymer (A) is a main component as a dispersant in the slurry composition of the present invention. The sulfonated (A) aliphatic diene (co) polymer is obtained by sulfonation of an aliphatic diene (co) polymer by a known method. Here, the aliphatic diene as a raw material of the component (A) is a hydrocarbon having 4 to 7 carbon atoms and containing two double bonds in the molecule, and examples of the aliphatic diene include: 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-
Heptadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 2,3-heptadiene, 2,5-heptadiene,
In addition to 3,4-heptadiene and 3,5-heptadiene, various branched dienes having 4 to 7 carbon atoms can be mentioned.
Preferably 1,3-butadiene, isoprene, 1,3-
It is pentadiene. These aliphatic dienes can be used alone or in combination of two or more.

The aliphatic diene constituting the component (A) of the present invention may be used in combination with another copolymerizable monomer (hereinafter referred to as "other monomer"). Other monomers include aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate. Alkyl esters of acrylic acid or methacrylic acid such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate; mono- or dicarboxylic acids or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid Anhydrides; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl chloride, vinylidene chloride, vinyl methyl ethyl ketone, vinyl methyl ether, vinyl acetate, vinyl formate, allyl acetate, methallyl acetate Unsaturated group-containing compounds such as acrylamide, methacrylamide, N-methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, acrolein and allyl alcohol; cyclic compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, styrene oxide, butylene oxide and the like. it can. These other monomers may be used alone or in combination of two or more. The amount of these other monomers used is 70% by weight or less, preferably 1 to 50% by weight, and more preferably 2 to 30% by weight, based on the total amount of the monomers.

The aliphatic diene-based (co) polymer used in the component (A) of the present invention means a polymer obtained by polymerizing at least one of the above aliphatic dienes, or another monomer. When used in combination with the body, it is a random or block type copolymer obtained by copolymerizing the above-mentioned aliphatic diene and another monomer. Such an aliphatic diene (co) polymer can be produced, for example, by the method disclosed in JP-A-2-227403.

The molecular weight of the aliphatic diene-based (co) polymer cannot be uniquely determined because the characteristics vary depending on the type and particle size of the solid fuel, but usually the polystyrene-equivalent weight average molecular weight is 300. ~ 500,000,
It is preferably 1,000 to 200,000.

The component (A) used in the present invention is
It can be obtained by sulfonating the aliphatic diene (co) polymer with a sulfonating agent. Here, examples of the sulfonating agent include sodium hydrogen sulfite, sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide (sulfuric anhydride), and a complex of sulfur trioxide and an electron-donating compound. Among these, sulfur trioxide, a complex of sulfur trioxide and an electron-donating compound, and the like are preferable.

Here, as the electron donating compound, N,
Ethers such as N-dimethylformamide, dioxane, dibutyl ether, tetrahydrofuran, diethyl ether; pyridine, piperazine, trimethylamine,
Amines such as triethylamine and tributylamine;
Sulfides such as dimethyl sulfide and diethyl sulfide; nitrile compounds such as acetonitrile, ethyl nitrile and propyl nitrile; and compounds that form a complex with sulfur trioxide, including N, N-
Dimethylformamide and dioxane are preferred. The above sulfonation reaction can be carried out, for example, by the method disclosed in JP-A-2-227403.

The cation species of the obtained sulfonated compound are not particularly limited, but in order to make it water-soluble, basic compounds such as hydrogen atom, alkali metal, alkaline earth metal, ammonium and amine are preferable.

The sulfonic acid content of the sulfonated product of the (A) aliphatic diene (co) polymer is preferably 3.5.
˜5.5 mmol / g, more preferably 4 to 5.3 mmol / g, and if it is less than 3.5 mmol / g, the dispersibility and mechanical stability of the slurry composition decrease, and
The amount of the component (A) required is large and the economy is poor. On the other hand, when it exceeds 5.5 mmol / g, the dispersibility and fluidity of the obtained slurry composition are deteriorated, which is not preferable.

The weight average molecular weight of the sulfonated product of the aliphatic diene-based (co) polymer (A) used in the present invention is not particularly limited, but is usually 1,000 to 1,000,
000, preferably 3,000 to 500,000, more preferably 5,000 to 100,000. When the weight average molecular weight is less than 1,000, the fluidity of the slurry cannot be maintained for a long period of time, while the amount of 1,000,000
If it exceeds, the slurry viscosity remarkably increases when the concentration of the solid fuel is increased, which becomes a problem.

Next, (B) lignin sulfonic acid (salt)
Mainly serves as a dispersant for the solid fuel in the composition of the present invention. This (B) lignin sulfonic acid (salt) is preferably used as an alkali metal salt and / or an alkaline earth metal salt of lignin.
Specific examples thereof include lithium salt, potassium salt, calcium salt, barium salt and the like.

Next, the clay minerals (C) play a role of mainly providing the stability of the slurry in the composition of the present invention. Specific examples of the (C) clay minerals include montmorillonite, nontronite, hectorite, vermiculite, and sepiolite.

In the solid fuel slurry composition of the present invention, the ratio of the above components (A) and (B) is (A) /
(B) (weight ratio) = 97/3 to 10/90 is preferable,
More preferably, it is 95/5 to 40/60. (A)
If / (B) (weight ratio) exceeds 97/3, the stability of the slurry may be problematic, whereas if it is less than 10/90, the viscosity of the slurry increases, which is a problem. Also, (A)
To (C) component ratio is [(A) + (B)] / (C)
(Weight ratio) = 95/5 to 10/90 is preferable, and 80/20 to 30/70 is more preferable. [(A) +
If the ratio (B)] / (C) (weight ratio) exceeds 95/5, the stability of the slurry may be problematic.
If it is less than 90, the viscosity of the slurry increases, which is a problem. Further, the total amount of the components (A) to (C) is preferably 0.05 to 3% by weight, more preferably 0.1 to 1.0% by weight in the slurry composition of the present invention. If it is less than 05% by weight, the stability of the slurry is poor and problems such as an increase in viscosity occur.

The solid fuel (D) used in the present invention is coal, petroleum coke, pitch or charcoal. Among these, the coal may be any of lignite, sub-bituminous coal, bituminous coal, anthracite and the like, and may be clean coal thereof without any particular limitation. Petroleum coke is residual coke obtained by distilling cracked oil by thermally decomposing asphalt, pitch, etc. obtained as a heavy residue by distillation during petroleum refining at a higher temperature, and generally contains an inorganic substance. Compared to coal, it is extremely hard to get wet with water. Furthermore, pitch is a heavy residue obtained by distilling a heavy residue during petroleum distillation and tar obtained by coal dry distillation to leave an oil content, and its softening point is 50 to 180 ° C.
Those having a temperature of less than 50 ° C. are difficult to grind. Pitch can be made into a high calorific value slurry fuel containing almost no ash and water as compared with coal.

The particle size of these (D) solid fuels may be any particle size as long as they are powders. However, the pulverized coal currently burned in a thermal power plant has a particle size of 70% by weight or more for 200 mesh pass. Since it is a thing, this granularity serves as a rough guide. However, the dispersants used in the present invention (A) to
The component (C) is not affected by the particle size and the type of solid fuel, and exerts an excellent effect on any solid fuel powder. The concentration of the solid fuel (D) in the composition of the present invention is usually 50 to 85% by weight, preferably 60 to 80% by weight.

Next, the type of (E) water is not particularly limited,
Tap water is used. (E) The amount of water used is (A)
The component (C) is used in the above proportion, and the solid fuel (D) in the composition is appropriately used within the above concentration range.

The method for producing the slurry composition of the present invention is not particularly limited, and it comprises mixing the components (A) to (E) by a desired method. For example, a method in which (D) solid fuel is previously pulverized by a dry method and then mixed in an aqueous solution in which components (A) to (C) which are dispersants are dissolved, and (D) solid fuel and (E) water are used as a slurry. After the preparation of (1), the components (A) to (C) which are dispersants are added, and (D) the solid fuel, (E) water and the components (A) to (C) which are dispersants are added to the mill. The method of mixing while crushing the solid fuel,
Any method can be implemented.

[0021]

EXAMPLES The present invention will be described more specifically below with reference to examples. In the examples,% is based on weight. Further, in the examples, various measurements were made according to the following. A 20% aqueous solution of a sulfonate having a sulfonic acid content was prepared, and a dialysis membrane [manufactured by Hanai Chemical Co., Ltd., Cellulose Diolize
r Tubing-VT351] was used to remove and purify low molecular weight substances, and this sample was used as a cation exchange resin [Amberlite IR-1 manufactured by Organo Corporation].
18 (H)] and ion-exchange to completely convert it into acid form,
The sulfonic acid content was determined by potentiometric titration.

Weight average molecular weight was measured by gel permeation chromatography (GPC) using polystyrene or sodium polystyrene sulfonate as a standard sample. The viscosity of the dispersible coal water slurry was measured at 25 ° C.

Static stability Coal water slurry was put in a 500 cc glass bottle, and the slurry properties after standing for 30 days were evaluated. That is, after standing still for 30 days, the glass bottle was tilted at 180 ° to remove the flowing out slurry, and then the amount (Z) of the slurry remaining at the bottom of the bottle and the concentration difference (Y) were evaluated. Z = {[amount of slurry remaining at bottom of bottle (g)] / [amount of slurry initially charged (g)] × 100 (%) Y = [coal concentration in slurry remaining at bottom of bottle (%)]
-[Coal Concentration (%) of Slurry Charged Initially] Calculated from the above formula, and when 0 <Z ≦ 20, ○, 20 <Z
When ≦ 30, it was evaluated as Δ, and when Z> 30, it was evaluated as x. Also, 0
The case where ≦ Y <3 was evaluated as ◯, the case where ≦ Y <5 was evaluated as Δ, and the case where Y ≧ 5 was evaluated as x.

Reference Example 1 A pressure resistant reactor was charged with 35.0 g of isoprene, 0.44 g of n-butyllithium and 200 g of cyclohexane, polymerized at 60 to 90 ° C. for 4 hours, and then 1 g of isopropyl alcohol (IPA) was added to polymerize. Stopped. Then, after distilling off the solvent and unreacted monomers under reduced pressure,
It was diluted with 50 g of 1,2-dichloroethane. Next, in a separate container, 150 g of dioxane and 45.
3 g was added while keeping the internal temperature at 25 ° C., and the mixture was stirred for 2 hours to obtain a sulfuric anhydride-dioxane complex. The complex obtained above was added to the polymer solution obtained above while maintaining the internal temperature at 10 ° C. over 1 hour. After the addition, stirring was continued for 2 hours, 25.0 g of sodium hydroxide and 150 g of water were added, and the mixture was stirred for 1 hour.
After stirring, water and the solvent were distilled off under reduced pressure to obtain the product, a yellow powdery product salt. This product is referred to as Polymer 1. The sulfonic acid content of this polymer was 4.9 mmol / g, and the weight average molecular weight was 20,000.

Reference Example 2 A pressure resistant reactor was charged with 35.0 g of 1,3-butadiene, 2 g of styrene, 0.44 g of n-butyllithium and 200 g of cyclohexane and polymerized at 60 ° C. for 2 hours and then isopropyl alcohol (IPA). 1 g was added to terminate the polymerization. Next, the solvent and unreacted monomers were distilled off under reduced pressure, and then diluted with 50 g of 1,2-dichloroethane. Next, sulfuric acid 3 was added to 100 g of dioxane in a separate container.
2.9 g was added while keeping the internal temperature at 25 ° C., and the mixture was stirred for 2 hours to obtain a sulfuric anhydride-dioxane complex. The complex obtained above was added to the polymer solution obtained above while maintaining the internal temperature at 25 ° C. over 2 hours. After the addition, stirring was continued for 2 hours, 18.0 g of sodium hydroxide and 150 g of water were added, and the mixture was stirred at 80 ° C. for 1 hour. After stirring, water and the solvent were distilled off under reduced pressure to obtain a product as a yellow powder sulfonate salt. This product is referred to as Polymer 2. The sulfonic acid content of this polymer was 5.1 mmol / g and the weight average molecular weight was 20,000.
Met.

Reference Example 3 Isoprene 35.0 g and styrene 3 were placed in a pressure resistant reactor.
g, n-butyl lithium 0.12 g, cyclohexane 2
After charging 00 g and polymerizing at 60 ° C. for 2 hours, 1 g of isopropyl alcohol (IPA) was added to terminate the polymerization. Next, the solvent and unreacted monomers were distilled off under reduced pressure, and the residue was diluted with 50 g of dioxane. Next, sulfuric acid 3 was added to 100 g of dioxane in a separate container.
2.9 g was added while keeping the internal temperature at 25 ° C., and the mixture was stirred for 2 hours to obtain a sulfuric anhydride-dioxane complex. The complex obtained above was added to the polymer solution obtained above while maintaining the internal temperature at 25 ° C. over 1 hour. After the addition, stirring was continued for 1 hour, 15.0 g of sodium hydroxide and 150 g of water were added, and the mixture was stirred at 80 ° C. for 1 hour. After stirring, water and the solvent were distilled off under reduced pressure to obtain a product as a yellow powder sulfonate salt. This product is referred to as Polymer 3. This polymer had a sulfonic acid content of 4.3 mmol / g and a weight average molecular weight of 75,000.
Met.

Examples 1 to 5 and Comparative Examples 1 to 5 Coal is made in Australia and contains 8 parts of 200 mesh pass.
A material containing 0%, 8.5% ash and 0.5% sulfur was used. The additives shown in Table 1 were put in water in advance, a predetermined amount of coal particles was gradually put therein, and the mixture was stirred at 3,000 rpm for 15 minutes by a homomixer to prepare a coal slurry having a concentration of 70%. In addition, the coal slurry thus obtained was evaluated. The results are shown in Table 1. As is clear from Table 1, the slurry composition of the present invention has a low viscosity and is excellent in stationary stability. On the other hand, when any one of the components (A) to (C) is lacking, it is found that there are drawbacks such that the slurry viscosity increases and the stability becomes poor.

[0028]

[Table 1]

[0029]

EFFECTS OF THE INVENTION The solid fuel slurry composition of the present invention has a low viscosity of the slurry, can increase the concentration of the solid fuel, and is excellent in stationary stability for a long period of time. Also,
The composition of the present invention is extremely economical and is most suitable for use as a fuel.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Ono 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd. (72) Inventor Akio Kai 717-1, Fukahori-cho, Nagasaki-shi, Nagasaki Prefecture No. Sanbishi Heavy Industries Co., Ltd. Nagasaki Research Institute (72) Inventor Hirohisa Yoshida 5-717-1, Fukahori-cho, Nagasaki-shi, Nagasaki Sanryo Heavy Industry Co., Ltd. Nagasaki Research Lab. No. 1 No. 1 Mitsubishi Heavy Industries Ltd. Nagasaki Shipyard

Claims (1)

[Claims] 1. A sulfonated product of (A) an aliphatic diene-based (co) polymer, (B) a ligninsulfonic acid (salt), and (C).
A solid fuel slurry composition containing clay minerals, (D) solid fuel, and (E) water as main components.