JPH0412757B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a coal slurry composition, and more particularly to a coal slurry composition that can reduce the amount of water as much as possible and maintain good fluidity. [Problems to be solved by the prior art and the invention] Today, with the diversification of energy sources, the time has come for coal to be reconsidered. However, since coal is a solid, there are many problems in its handling and use, such as transportation, storage, and combustion. In particular, when coal is used as a fuel, it is usually pulverized to improve the combustion speed and combustion efficiency, but this pulverized coal can scatter fine particles into the atmosphere and cause pollution. In addition, there are various disadvantages such as the risk of spontaneous combustion, transport from coal mining areas, and storage in coal yards. Therefore, in order to overcome transportation problems, so-called coal-water slurry, in which powdered coal is dispersed in water, has been partially put into practical use. However, if the amount of water is reduced and the coal concentration is increased, this coal-water slurry becomes a coagulum with no fluidity, so it is desirable to reduce the amount of water as much as possible and ensure good fluidity. It is rare. Conventionally, sodium salts of sulfonated styrene-maleic anhydride copolymers have been known as fluidizing agents used for such purposes. However, this copolymer is a copolymer of sulfonated styrene and maleic anhydride in an equimolar ratio (1:1) or less, and is still unsatisfactory in its fluidity imparting function. [Means for Solving the Problems] The present inventors have conducted extensive research in order to solve the above-mentioned conventional problems. As a result, we found that by using a specific compound as a fluidizing agent, a coal slurry composition that can reduce the amount of water as much as possible and maintain good fluidity can be obtained. He has completed his invention. That is, the first aspect of the present invention is a saponified product of (A) pulverized coal, (B) water, and (C) a sulfonated styrene-maleic acid copolymer, in which the molar proportion of sulfonated styrene units to maleic acid units is The present invention provides a coal slurry composition comprising: Further, the second aspect of the present invention is further added to the first aspect of the present invention.
Component (D) is formalin condensate of naphthalene sulfonate, olefin-unsaturated dicarboxylate copolymer, polyoxyethylene compound, lignin sulfonate, sulfonated melamine resin salt, formalin of sulfonated creosote oil. The present invention provides a coal slurry composition containing one or more compounds selected from the group consisting of a salt of a condensate, polyvinyl alcohol, and an α-olefin sulfonate. In the present invention, powdered coal is used as component (A). Here, the coal is not particularly limited and various coals can be used, including lignite, subbituminous coal, bituminous coal, anthracite, and the like. Powdered coal used as component (A) is made by crushing such coal into powder, and usually has an average particle size of 10 to 10.
It is 100μ. Next, in the present invention, water is used as component (B). The water used as component (B) here is the water used as component (A) above.
It is sufficient to use as little amount as possible for the powdered coal that is the component, and usually 20 to 100 parts by weight for 100 parts by weight of component (A).
A proportion of 200 parts by weight is sufficient. Furthermore, in the present invention, component (C) is a saponified product of a sulfonated styrene-maleic acid copolymer, and the molar fraction of sulfonated styrene units is 50%.
Use one with an amount exceeding . Here, the saponified product of sulfonated styrene-maleic acid copolymer has the following general formula: A sulfonated styrene unit [] and (wherein, X ¹ is either Na, K, 1/2Ca, NH ₄ or an organic amino group) general formula It has a maleic acid unit [ ] represented by (wherein, X ² and X ³ are either Na, K, 1/2Ca, NH ₄ or an organic amino group). Here, in the present invention, the mole fraction of sulfonated styrene units [] in the saponified product of the above-mentioned copolymer is more than 50%, preferably the mole fraction of sulfonated styrene units [] is 55 to 50%. 70% is used. Here, the mole fraction of sulfonated styrene units [] is
If it is less than 50%, the obtained coal slurry composition will not have sufficient fluidity, which is not preferable. The saponified product of the sulfonated styrene-maleic acid copolymer used in the present invention has the above-mentioned sulfonated styrene unit [] and maleic acid unit [], and a random copolymer of these,
There are various types such as block copolymers and alternating copolymers. The degree of polymerization of the saponified product of the sulfonated styrene monomaleic acid copolymer having the above sulfonated styrene units [] and maleic acid units [] is usually 4.
~10. The saponified product of the above-mentioned sulfonated styrene-maleic acid copolymer can be obtained by, for example, sulfonating a styrene-maleic acid copolymer using a conventional method, removing the unreacted copolymer, and then removing the remaining sulfuric acid using a normal liming saw. It can be obtained by saponification, such as removal of gypsum by washing. The styrene-maleic acid copolymer may be either a random copolymer or a block copolymer, and has a number average molecular weight of 1000 to 1000.
9000, preferably 1500-2000. The amount of component (C) above is 0.1 to 5.0 per 100 parts by weight of component (A).
It is used in a proportion of 0.2 to 4.0 parts by weight, preferably 0.2 to 4.0 parts by weight. If the blending ratio of component (C) is less than 0.1 part by weight, the resulting composition will not form a slurry, which is not preferable. Further, even if component (C) is blended in an amount exceeding 5.0 parts by weight, an effect commensurate with the blended amount cannot be obtained. The first aspect of the present invention consists of the three components (A), (B), and (C) as described above. Next, the second aspect of the present invention is one in which the first aspect of the present invention, which consists of the three components (A), (B), and (C), is further blended with component (D). Here, component (D) in the second aspect of the present invention is a formalin condensate of naphthalene sulfonate, an olefin-unsaturated dicarboxylate copolymer, a polyoxyethylene compound, a lignin sulfonate, a sulfonated melamine resin salt, It is one or more compounds selected from the group consisting of polyvinyl alcohol and α-olefin sulfonate. Here, the formalin condensate of naphthalene sulfonate has the following general formula: (In ^the _formula , X ⁴ and By reacting and further saponifying the obtained reaction product with sodium hydroxide, calcium hydroxide, potassium hydroxide, etc.
Alternatively, it can be obtained by treatment with an ammonium group or an organic amino group. Note that sodium is particularly preferred as X ⁴ and X ⁵ in the above general formula. It is also possible to use mixed naphthalenes containing up to 30 mol% of alkylnaphthalenes. Next, the olefin-unsaturated dicarboxylate copolymer has the following general formula: (In the formula, X ⁶ and X ⁷ are either Na, K, 1/2Ca, NH ₄ or an organic amino group, A represents an olefin, B represents an unsaturated dicarboxylic acid residue, and l ² is 0.4 to 0.6, m is 2 to 300, preferably 3 to 60), and can be obtained, for example, by reacting maleic anhydride and isoamylene in the presence or absence of a solvent. I can do it. Here, the olefin is not particularly limited, and examples thereof include ethylene, propylene, butene-1, butene-2, isobutylene, pentene-1, pentene-1, and pentene-1.
2,2-methylbutene-1,2-methylbutene-
Examples include 2,4-methylbutene-1, hexene-1, hexylene, heptylene, octylene, and the like. Further, the unsaturated dicarboxylic acid is not particularly limited, and examples thereof include maleic acid, citraconic acid, itaconic acid, and aconitic acid. Next, the polyoxyethylene compound may be a compound having a component of ( _-CH2CH2O ) _-o1 (in the formula, ⁿ¹ represents a real number from 1 _to 40).
Specifically, polyoxyethylene alkyl phenyl ether (e.g. polyoxyethylene nonyl phenyl ether), polyoxyethylene polyaralkyl phenyl ether, polyoxyethylene bisphenol A ether, polyoxyethylene alkyl ether (e.g. polyoxyethylene lauryl) ether, etc.), polyoxyethylene polyoxypropylene block polymers (e.g. polyoxyethylene polyoxypropylene condensates, etc.),
Polyoxyethylene secondary alcohol ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester,
Examples include polyoxyethylene alkylamine polyoxyethylene alkyl sulfate salts, among which polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether and polyoxyethylene polyoxypropylene block polymer are preferred. Furthermore, lignin sulfonate is a salt of a lignin derivative obtained when wood or other lignin-containing raw materials are treated with sulfite, bisulfite, sulfite, etc., and has the following general formula: (In the formula, X ⁸ represents any one of Na, K, 1/2Ca, NH ₄ and an organic amino group.) In addition, the sulfonated melamine resin salt has the following general formula: ₍ ^{wherein ,} It can be obtained by subjecting melamine to a condensation reaction. Further, as the component (D), salts of polymarin condensates of sulfonated creosote oil, polyvinyl alcohol, and α-olefin sulfonates may be mentioned, and one or more types selected from the group consisting of the above compounds may be mentioned. using compounds. Furthermore, conventional fluidizing agents such as hydrogenated oligosaccharides can also be used. The above (D) component is based on 100 parts by weight of the above (A) component,
It is used in a proportion of 0.01 to 0.2 parts by weight. The coal slurry composition of the present invention is a mixture of the above-mentioned components, and is usually obtained by mixing the above-mentioned components using a known mixer. [Effects of the Invention] According to the first aspect of the present invention as described above, pulverized coal
A coal slurry composition can be obtained in which the amount of water used can be as small as 20 to 200 parts by weight per 100 parts by weight, and which can maintain good fluidity. Furthermore, according to the second aspect of the present invention, a coal slurry composition having better fluidity can be obtained. Therefore, the present invention can be effectively utilized in the coal industry, coal chemical industry, etc. [Example] Next, the present invention will be explained with reference to an example. Production example 1 Styrene-maleic acid copolymer (number average molecular weight
1600, manufactured by ARCO Chemical, "SMA-1000")
Dissolve 85g in 100ml of 98% concentrated sulfuric acid, add 50ml of fuming sulfuric acid.
Add g over 1 hour while adjusting the temperature to 30-40℃,
Thereafter, the copolymer was reacted for 3 hours to sulfonate the copolymer. After the reaction was completed, water was added to the reaction mixture to separate the unreacted styrene-maleic acid copolymer, and then heated at 70°C.
The remaining sulfuric acid was removed as a gypsum component by a conventional liming sodation method to obtain 126 g of a saponified product (sodium salt). The yield was 92%.
The molar fraction of sulfonated styrene units in this saponified sulfonated styrene-maleic acid copolymer was 43.8%. Production Example 2 A styrene-maleic acid copolymer with a number average molecular weight of 1700, manufactured by ARCO Chemical, “SMA-
128 g of a saponified product (sodium salt) was obtained in the same manner as in Production Example 1, except that "2000" was used and the amount of fuming sulfuric acid used was 70 g (yield: 90%). The molar fraction of sulfonated styrene units in this saponified sulfonated styrene-maleic acid copolymer was 57.6%. Production Example 3 A styrene-maleic acid copolymer with a number average molecular weight of 1900, manufactured by ARCO Chemical, “SMA-
3000'' and the amount of fuming sulfuric acid used was 80 g, 115 g of saponified product (sodium salt) was obtained in the same manner as in Production Example 1 (yield: 85%). The molar fraction of sulfonated styrene units in this saponified sulfonated styrene-maleic acid copolymer was 63.2%. Production example 4 Production of formalin condensate of naphthalene sulfonate (component a) 100 g of β-methylnaphthalene and 400 g of naphthalene
Add 600g of 98% sulfuric acid to the solution and treat at 160℃ for 1.5 hours.
Sulfonated. Next, 310 g of 37% formalin was added dropwise at 100°C, and condensation was carried out for 5 hours. At this time, when the viscosity increased, a small amount of water was added to lower the viscosity and condensation was performed. The obtained cocondensate was made into a sodium salt by a conventional liming sodation method. Production Example 5 Production of olefin-unsaturated dicarboxylate copolymer (component b) A mixture of 98 g of maleic anhydride, 70 g of isoamylene, 4 g of azobisisobutyronitrile, and 600 g of benzene was heated at 70°C under a nitrogen atmosphere using an autoclave. The mixture was stirred and reacted under pressure for 8 hours.
After the reaction was completed, the precipitated copolymer was separated to obtain a dried isoamylene-maleic acid copolymer (number average molecular weight: 2800). 1.2 equivalents of aqueous sodium hydroxide solution was added to this copolymer, and the mixture was heated and stirred to obtain a sodium salt. Production Example 6 Production of lignin sulfonate (component d) Sulfite pulp waste liquid was oxidized with hydrogen peroxide under alkaline conditions, and then purified by ultrafiltration (molecular weight cut off: 1000). Production Example 7 Production of sulfonated melamine resin salt (component e) In a glass reactor, 76 g of a 37% formalin aqueous solution adjusted to pH 8 with sodium carbonate and 29 g of melamine.
and heated to 70℃. After 5 minutes, the melamine was completely dissolved and the reaction solution became transparent. The reaction mixture was immediately cooled, and 48 g of water and 25 g of sodium sulfite were added while maintaining the temperature of the reaction liquid at 45°C. Thereafter, the temperature was raised to 80°C and reaction was carried out for 20 hours to obtain a sulfonated melamine resin salt. Production Example 8 Production of salt of formalin condensate of sulfonated creosote oil (component f) Add 600 g of 98% sulfuric acid to 500 g of creosote oil,
Sulfonation was carried out at 150°C. followed by concentration 37%
310 g of formalin was added dropwise and condensation was carried out at 100°C for 5 hours. The obtained co-condensate was subjected to liming sodation in a conventional manner to obtain a sodium salt of a formalin condensate of a sulfonated creosote oil. Examples 1 to 12 and Comparative Examples 1 and 2 A predetermined amount of powdered coal and water having the properties shown in Table 1 and the particle size shown in Table 2 were mixed at 40 rpm for 30 minutes using a twin-shaft Z-blade mixer. Then, a specified fluidizing agent shown in Table 3 was added and mixed for an additional 30 minutes to prepare a coal slurry composition. The viscosity of the obtained composition was measured to evaluate its fluidity. The conditions and results are shown in Table 3.

【table】

【table】

[Table] *1 Polyoxyethylene nonyl phenyl ether

40% aqueous solution of

*2 Polyvinyl alcohol
(−CH ₂ −CH)− ₂₀
｜
OH
*3 α-olefin sulfonate
_C10 -CH=CH _{( CH2} ) _5SO3Na

Claims (1)

[Claims] 1. A saponified product of (A) pulverized coal, (B) water and (C) a sulfonated styrene-maleic acid copolymer, wherein the molar fraction of sulfonated styrene units is 50%. A coal slurry composition comprising: 2. The coal slurry composition according to claim 1, comprising 100 parts by weight of component (A), 20 to 200 parts by weight of component (B), and 0.1 to 5.0 parts by weight of component (C). 3 (A) Powdered coal, (B) water, (C) sulfonated styrene
Saponified products of maleic acid copolymers in which the molar fraction of sulfonated styrene units exceeds 50%, and (D) formalin condensates of naphthalene sulfonates, olefin-unsaturated dicarboxylate salts, etc. Polymers, polyoxyethylene compounds, lignin sulfonates, sulfonated melamine resin salts,
A coal slurry composition comprising one or more compounds selected from the group consisting of a salt of a formalin condensate of a sulfonated creosote oil, polyvinyl alcohol, and an α-olefin sulfonate.