JPH0367555B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a pitchi-water slurry composition with good fluidity in which pitchi powder is stably dispersed in water. Conventional technology Traditionally, the energy structure has been based on petroleum, but as energy diversification has begun to be attempted beyond so-called oil shocks, solid fuels such as coal have begun to be reconsidered. Ta. However, since solid fuels such as coal are solid unlike liquid fuels such as oil, it is difficult to transport them by ordinary pipelines, tank trucks, etc. For this reason, as a means of transporting these solid fuels, a method has been proposed in which the solid fuels are pulverized and mixed with water to form a slurry composition. Problems to be Solved by the Invention However, in such a slurry composition, when the concentration of the solid fuel is increased, the viscosity of the composition increases and the fluidity deteriorates, while when the concentration is decreased, stabilization of the slurry is hindered. This has problems such as poor combustion efficiency. As a result of intensive studies to obtain a slurry composition capable of efficiently transporting a solid fuel with a high energy content, the inventors of the present invention discovered that they could use pitch powder as the solid fuel and combine a specific compound as a dispersant. It has also been discovered that a slurry composition with high energy content and good stability and fluidity can be obtained by the method, and the present invention has been achieved based on this finding. Means for Solving the Problems That is, the present invention has a tricyclodecane skeleton and/or
Alternatively, the present invention provides a pitchi-water slurry composition characterized in that pitchch powder is dispersed in water using a compound having a tricyclodecene skeleton and a sulfone group bonded thereto as a dispersant. Pitch, the high-energy solid fuel used in the present invention, is a black carbonaceous solid residue obtained when distilling tar obtained by dry distillation of coal, or a distillation kettle obtained when petroleum is vacuum distilled. Residual oil or similar material, soft pitch (softening point 50-60℃), medium pitch (softening point 60-75℃)
℃), and hard pitch (softening point of 90℃ or higher). The softening point of pitch is preferably 50 to 180°C, more preferably 60 to 180°C, and if it is less than 50°C, it does not fall into the category of pitch and is difficult to powder. Unlike coal, such pitch contains almost no water or ash, making it a high-energy fuel. However, in order to form a slurry composition,
Such pitch must also be pulverized, and in the present invention, pitch obtained from coal or petroleum is first pulverized by conventional wet or dry, preferably wet, pulverizing means. The smaller the particle size of the pitch powder, the easier the slurry will be dispersed and stabilized, and the combustion efficiency will be better, but on the other hand, the viscosity of the slurry will increase. Therefore, the particle size of the pitch powder of the present invention is not particularly limited, but 50 to 90% by weight of the powder that passes through 200 meshes, which is similar to the particle size of pulverized coal used in current pulverized coal boilers. It is preferable to use something of about 100%. Pitch contains a large amount of polycyclic aromatic polymer substances that are soluble in organic solvents in addition to free carbon, and has no affinity for water. Therefore, adding pitchi powder to water does not result in a stable slurry composition. Therefore, by adding a surfactant as a dispersant, the active agent is adsorbed to the interface between pitchi particles and water, which causes aggregation of pitchi particles. Measures have been taken to prevent this and obtain a slurry composition that is stably dispersed. The present invention focuses on the composition of pitch and uses the following specific compound as a dispersant to provide a slurry composition with extremely high concentration, low viscosity, and a good dispersion state. In the present invention, the tricyclodecane skeleton or tricyclodecene skeleton is shown below [(A), (B)]. (i.e. tricyclo[5.2.1.0 ^2.6 ]decane or decene) Dispersants that can be used in the present invention include the following compounds. (i) A sulfonated product obtained by sulfonating a polymer obtained by polymerizing cyclopentadiene or a cyclopentadiene derivative represented by the general formula (a) or (b) as shown in JP-A-58-152861. . (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) (In the formula, R ₂ and R ₃ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) (ii) General formula (a) as shown in JP-A-58-152862 or a sulfonated product obtained by sulfonating a reaction product mixture obtained by reacting cyclopentadiene represented by general formula (b) or a cyclopentadiene derivative with a compound represented by general formula (c), or the sulfone Condensation product of chemical substances. (In the formula, R ₄ and R ₅ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) (iii) In the general formula (d) as shown in JP-A-58-152860, A condensate obtained by condensing the sulfonated cyclopentadiene derivative. (In the formula, R ₆ , R ₇ and R ₈ are the same or different,
represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ₉ and R ₁₀ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n is 1
or 2, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or an amine. ) (iv) Polymers or copolymers of sulfonated dicyclopentadiene (e) as shown in JP-A-59-64608. (In the formula, n and M are the same as in formula (d).) (v) A sulfonated product of hydroxydicyclopentadiene represented by the general formula (f) as shown in Japanese Patent Application No. 58-43729. Polymer or copolymer of. (In the formula, n and M are the same as in formula (d).) (vi) A disulfonated product of a dicyclopentadiene derivative represented by the general formula (g) as shown in the specification of Japanese Patent Application No. 58-42205. A condensate obtained by condensing. (In the formula, R ₁₁ and R ₁₂ are the same or different,
It represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and n and M are the same as in formula (d). ) Among these (i) to (vi), the compound (iv) above is particularly preferred. In the above (i), specific compounds that can be represented by general formula (a) or general formula (b) include, for example, cyclopentadiene, alkylcyclopentadiene such as methylcyclopentadiene, ethylcyclopentadiene, and propylcyclopentadiene. , or a dimer formed by any combination of these, such as dicyclopentadiene, and preferred examples include cyclopentadiene, dicyclopentadiene, or a mixture of both. Specific compounds that can be represented by the general formula (c) in (ii) above include, for example, benzene, toluene, xylene (o-, m-, p-), ethylbenzene, n-propylbenzene, iso-propyl Benzene, methylethylbenzene (o-, m-,
p-), n-butylbenzene, sec-butylbenzene, tert-butylbenzene, iso-propyltoluene (o-, m-, p-), amylbenzene, hexylbenzene, amyltoluene (o-, m-,
Examples include benzene derivatives such as mono- or dialkyl-substituted benzenes such as p-), particularly preferred are benzene, toluene, xylene,
Examples include propylbenzene and butylbenzene. Next, a method for producing the dispersant used in the present invention will be explained. However, the methods for manufacturing the dispersants (i) to (vi) above are disclosed in JP-A-58-152861 and JP-A-58-1999, respectively.
It is described in detail in Japanese Patent Application No. 152862, Japanese Patent Application Laid-Open No. 152860-1980, Japanese Patent Application Laid-open No. 64608-1982, Japanese Patent Application No. 43729-1982, and Japanese Patent Application No. 42205-1987. An example of the production of dispersant (i) will be explained. Cyclopentadiene or a cyclopentadiene derivative [general formula (a) or (b)] is treated with an acidic compound catalyst (for example, sulfuric acid, phosphoric acid, hydrogen fluoride, boron trifluoride and its complexes, aluminum chloride, aluminum bromide, tin chloride, zinc chloride, titanium trichloride, etc.) and, if necessary, a solvent such as hydrocarbons or halogenated hydrocarbons, usually at a reaction temperature of -20 to 150°C for several hours. A polymer is obtained by a polymerization reaction. The polymer is preferably treated in the presence of an inorganic oxidizing agent (e.g., nitrates, nitrites, etc.) and a solvent (e.g., water, methyl alcohol, ethyl alcohol, etc.), usually at a reaction temperature of 50 to 200°C, at normal pressure or under elevated pressure. A sulfonation reaction is carried out under pressure using a sulfonating agent such as an acidic sulfite, metasulfite, or sulfite of an alkali metal alone or in a mixture to obtain a sulfonated product. From the viewpoint of ease of sulfonation of the polymer, the preferred number average molecular weight is 10,000.
Below, it is particularly preferably 300 to 5000. The sulfonated product is usually one in which 20 to 100% of the remaining double bonds in the polymer are sulfonated, and the degree of sulfonation is determined by converting the obtained sulfonated product into an acid form by an ion exchange method. It can be determined by alkaline titration. The degree of sulfonation is 50 in terms of foaming etc.
% or more, more preferably 70% or more, particularly preferably 90% or more. The sulfonated product can be converted into an acid form, an alkali metal, alkaline earth metal, ammonium salt, or amine salt by an ion exchange method or a neutralization reaction. The following dispersants (co)polymers or condensates produced with (ii) to (vi) can also be used in the same manner. Next, an example of the production of dispersant (ii) will be explained. Cyclopentadiene or cyclo A reaction product mixture is obtained by reacting a pentadiene derivative [general formula (a) or (b)] with a compound of general formula (c) in the presence of the above-mentioned acidic compound catalyst and solvent at a reaction temperature of usually -20 to 150°C. The reaction product mixture is a reaction product obtained by adding one molecule of the compound represented by the general formula (c) to one molecule of dicyclopentadiene, and a reaction product obtained by adding one molecule of the compound represented by the general formula (c) to two molecules of dicyclopentadiene. In addition to several types of adducts such as reaction products to which one molecule of the compound represented by is added, polymers of cyclopentadienes and/or dicyclopentadienes and compounds represented by the above general formula (c) to the polymers. It is a mixture of various compounds such as the reaction product added with (the number average molecular weight of the reaction product mixture is
10,000 in terms of ease of the sulfonation reaction described below.
The following are preferred. ) The reaction product mixture is sulfonated by the same method as the polymer sulfonation method described in the method for producing the dispersant (i) to obtain a sulfonated reaction product mixture. The sulfonated product is used as a condensation monomer, and if necessary, other condensation monomers such as benzene, toluene, xylene, and phenol are used in combination with an acidic compound catalyst (for example, sulfuric acid). A condensate is obtained by condensing with an aldehyde (for example, formaldehyde) using usually 0.0001 to 10 times the total mole number. The number average molecular weight of the condensate is preferably 500 to 30,000 from the viewpoint of pitch dispersion effect. Next, an example of manufacturing the dispersant (iii) will be explained. Compounds represented by the following general formula (h) (e.g. benzene, toluene, xylene, propylbenzene,
butylbenzene, etc.) and a compound represented by general formula (i) (e.g., dimer of cyclopentadiene, methylsillopentadiene, ethylcyclopentadiene, etc.) with a catalyst (e.g., sulfuric acid, phosphoric acid, hydrogen fluoride, trifluoride, etc.). The Friedel-Crafts reaction is carried out in the presence of boron and its complexes, aluminum chloride, aluminum bromide, etc., preferably at 0 to 100°C for 1 to 5 hours, to obtain a compound represented by general formula (j). (R ₆ , R ₇ , and R ₈ are the same in the general formula (d) above) (R ₉ and R ₁₀ are the same as in the general formula (d) above) (R ₆ , R ₇ , R ₈ , R ₉ , and R ₁₀ are the same as in the general formula (d) above) The compound represented by the general formula (j) is Sulfonation is carried out in the same manner as the sulfonation method for combination, and then, if necessary, an alkali metal, an alkaline earth metal, ammonium, amines, etc. are used to form a sulfonate, so that the general formula (d) is obtained. A sulfonated product of the represented cyclopentadiene derivative is obtained. The sulfonated product is subjected to a condensation reaction in the same manner as the method for producing the condensate explained in the method for producing the dispersant (ii) to obtain a condensate. In the general formula (d), when M is a hydrogen atom, an alkali metal, ammonium or an amine,
When n=1 and M is an alkaline earth metal,
n=2. Examples of the alkali metal include sodium and potassium, and examples of the amine include alkylamines such as methylamine, ethylamine, propylamine, dimethylamine, trimethylamine, triethylamine, butylamine, dibutylamine, and tributylamine, ethylenediamine, diethylenetriamine, and tributylamine. Examples of the alkaline earth metal include polyamines such as ethylenetetramine, morpholine, and piperidine, and examples of the alkaline earth metal include calcium, magnesium, and zinc. Further, these M can be mutually exchanged with other types of M by various ion exchange techniques or neutralization reactions. Next, an example of manufacturing the dispersant (iv) will be explained. The compound is obtained by sulfonating dicyclobentadiene in the same manner as the polymer sulfonation method described in the method for producing dispersant (i), and then converting it into a sulfonate salt if necessary. The compound is subjected to a polymerization reaction in the same manner as the method for producing the polymer explained in the method for producing the dispersant (i) to obtain a polymer. In addition, in the polymerization reaction, if a copolymerizable monomer such as an aliphatic, alicyclic, or aromatic hydrocarbon having an olefinic double bond is present, a copolymer can be obtained. The number average molecular weight of the polymer or copolymer is preferably 500 or more, from the viewpoint of pitch dispersion effect.
More preferably 2000 or more, most preferably 3500~
50000. Next, an example of the production of the dispersant (v) will be explained. The method for producing dispersant (iv) is the same as that for producing dispersant (iv), except that hydroxydicyclopentadiene is used instead of dicyclopentadiene, which is the starting material for producing dispersant (iv). The number average molecular weight of the polymer or copolymer is preferably 500 or more, from the viewpoint of pitch dispersion effect.
Most preferably it is 1500-50000. Next, an example of manufacturing the dispersant (vi) will be explained. For example, sodium bisulfite is added to the reaction product obtained by reacting dicyclopentadiene and benzene or a benzene derivative by Friedel-Crafts reaction in the presence of a BF ₃ catalyst, and if necessary, sulfonic acid is added to the reaction product. A compound of general formula (k) can be obtained by the salt method. (R ₁ , R ₂ are the same as in the general formula (g), n,
M is the same as formula (d)) The compound of general formula (k) is mixed with sulfuric acid such as sulfuric acid, sulfuric anhydride, and fuming sulfuric acid (the amount of sulfuric acid used is according to the general formula (k). ) Preferably 0.1 to 5 times the mole number of the compound)
When the reaction is carried out at 50 to 150°C, a disulfonated product of general formula (g) is obtained. A condensate is obtained by condensing the disulfonated product using the same condensation method as explained in the method for producing dispersant (ii). One or more of the above-mentioned dispersants may be used as a pitch dispersant, if necessary in combination with surfactants, additives, etc. described later. Examples of surfactants that can be used as needed in the slurry composition of the present invention include polycarboxylic acid-based, polyacrylamide-based, polyester-based, etc.
A nonionic surfactant, an anionic surfactant, etc. can also be used in combination to lower the surface tension. Further, an antifoaming agent or the like may be added as necessary. The amount of the dispersant shown in (i) to (vi) above to be added to the slurry composition is 0.05 to 5% by weight, preferably 0.1% by weight based on the pitch powder, although it depends on the type and particle size of the pitch powder. ~2% by weight. If the amount of the dispersant added is less than 0.05% by weight, the viscosity reduction and dispersion stability of the slurry composition will not be sufficient, while if it exceeds 5% by weight, the above effects will not be proportionally large, and on the contrary, Viscosity may increase or dispersion stability may deteriorate. The concentration of pitch powder can be increased by adding the above-mentioned dispersant, but it is usually in the range of 50 to 90% by weight, preferably 60 to 85% by weight, based on the entire slurry composition. Effect: When the dispersant of the present invention is present in the pitch-water slurry composition, the dispersant is adsorbed onto the surface of pitch particles, and the resulting electrostatic force and relatively large steric hindrance of the dispersant itself prevent pitches from approaching each other. hindered,
As a result, the viscosity of the composition can be reduced and stable dispersibility can be obtained. Examples Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that % in the examples is based on weight. In addition, the weight average molecular weights described in the examples are calculated by converting the results measured by GPC (gel permeation chromatography) using a calibration curve created using several types of polystyrene sulfonic acids with different molecular weights as standard substances. It is something. The eluent was a mixture of acetonitrile and 0.5 N Na ₂ SO ₄ aqueous solution at a weight ratio of 3:7, and the column was TSK-GEL manufactured by Toyo Soda Co., Ltd.
G3000SW and TSK-GEL G2000SW were connected in series and measured using a UV detector. The following formula (a) was calculated from the obtained GPC chart to determine the weight average molecular weight. Σ [(molecular weight) x (area)] / total area... (a) Reference example 1 3000 g of dicyclopentadiene, 1888 g of sodium bisulfite, and 91.7 g of potassium nitrate in a stainless steel autoclave with a capacity of 30 and equipped with a stirring device and a thermometer. Add 12 g of isopropyl alcohol and 3000 g of distilled water, supply nitrogen at room temperature until the internal pressure in the autoclave reaches 1.0 Kg/cm ² (gauge pressure), close the valve, and add 110 g of distilled water while mixing under strong stirring. The reaction was allowed to proceed at ℃ for 5 hours. After that, it was allowed to cool to room temperature, and most of the isopropyl alcohol was removed by distillation, then distilled water and petroleum ether were added and mixed thoroughly, the separated petroleum ether and precipitate were removed, and the resulting aqueous layer was concentrated. , distilled to dryness. This was dissolved in glacial acetic acid, and the acetic acid insoluble portion consisting of inorganic salts was separated using a centrifuge. The obtained acetic acid soluble portion was concentrated to dryness and thoroughly washed with acetone to obtain 2800 g of a white solid. This is sulfonated compound A

Let it be [formula]. Next, 1.5 kg of the above-mentioned sulfonated compound A, 1.0 kg of sulfuric acid, and 0.5 kg of water were placed in a glass-lined autoclave (No. 5) equipped with a stirring device, and heated at 120°C.
The polymerization reaction was carried out for 6 hours. After the reaction was completed, liming was performed with CaCO ₃ to remove sulfuric acid, and the solid content obtained was 1.4 kg. This product was a polymer (hereinafter referred to as Polymer A) with a weight average molecular weight of 8,850. The surface tension of a 4% aqueous solution of the polymer was 69.7 dyn/cm. Reference Example 2 A polymer was produced under the same conditions as in Reference Example 1, except that the polymerization temperature in Reference Example 1 was changed from 120°C to 130°C. The weight average molecular weight of the obtained polymer (hereinafter referred to as polymer B) was 13,400.
The surface tension of a 4% aqueous solution of was 70.6 dyn/cm. Reference Example 3 A polymer was produced under the same conditions as in Reference Example 1, except that the polymerization temperature in Reference Example 1 was changed from 120°C to 100°C. The weight average molecular weight of the obtained polymer (hereinafter referred to as Polymer C) was 2200, and the surface tension of a 4% aqueous solution of Polymer C was 64.8 ddyn/cm. Reference Example 4 1.5 kg of sulfonated compound A used in the polymerization reaction in Reference Example 1 was mixed with 0.15 kg of acrylic acid and sulfonated compound
Polymerization was carried out under the same conditions as in Reference Example 1 except that 1.35 kg of the mixture was used to obtain a copolymer. The weight average molecular weight of the obtained copolymer (hereinafter referred to as copolymer A) was 5,700. Reference Example 5 In Reference Example 1, 24 g of the obtained polymer A was added to water.
The solution was dissolved in 1,000 g of a strongly acidic cation exchange resin that had been converted into an acid form, and after standing for a day and night, the resin was filtered off and the filtrate was dried.
The obtained solid content (hereinafter referred to as polymer D) was 21
It was hot at g. Next, when Polymer D was subjected to neutralization titration with NaOH, it was neutralized with an equivalent amount of NaOH. From these results, it can be seen that in the polymer D obtained after the cation exchange treatment, M=H in the general formula (e), which was converted to M=Na after neutralization. Reference Example 6 Polymer D obtained in Reference Example 5 was treated with KOH, Ca
When neutralized with (OH) ₂ , aqueous ammonia, and monoethanolamine, the neutralization was completed in equivalent amounts. The water was removed under reduced pressure to separate the polymer. These are polymers of K (hereinafter referred to as polymer E), Ca (hereinafter referred to as polymer F), ammonia (hereinafter referred to as polymer G), and monoethanolamine salt (hereinafter referred to as polymer H). It is a combination. Reference Example 7 In Reference Example 2, a polymer was produced using a polymerization time of 20 hours. The weight average molecular weight of the obtained polymer (hereinafter referred to as polymer) was 19000,
The surface tension of this 4% aqueous solution was 72.6 dyn/cm. Examples 1 to 12, Comparative Examples 1 to 4 Pitch adjustment Types of pitch L with different softening points (softening points 67 to 72
), M (softening point: 82 to 85°C), and N (softening point: 120°C) were dry-pulverized in a sample mill to obtain pitch powder. Table 1 shows the particle size of this pitch fine powder.

[Table] Pitzchi - Preparation of water slurry composition Dispersant A obtained in Reference Examples 1 to 7 in advance in water
~ I or a known dispersant is added, and a predetermined amount of the fine powder shown in Table 1 is added thereto, and the mixture is stirred at 3000 rpm for 15 minutes using a homomixer to obtain a pitch-water slurry composition with a desired concentration. Adjusted things. The viscosity of the Pitzchi water slurry composition thus obtained was measured at 25°C. Thereafter, the composition was allowed to stand and the viscosity was measured over time to examine the stability of the slurry composition. The results are shown in Table 2. As is clear from Table 2, it can be seen that the pitcher water slurry composition using the dispersant of the present invention has extremely excellent slurry dispersibility and slurry stability. Further, no foaming of the slurry was observed.

【table】

[Table] Effects of the Invention By selecting the above-mentioned specific compound as a dispersant, the pitch-water slurry composition of the present invention can lower the viscosity of the slurry compared to the conventional technology. Concentration can be increased. Furthermore, the slurry has good dispersibility and fluidity, and has little foaming property, making it suitable for transportation by pipeline. Furthermore, since it uses pitch as the solid fuel, it has the advantage of high energy and little ash remaining after combustion.

Claims (1)

[Claims] 1. A pitchi-water slurry composition characterized in that pitchi powder is dispersed in water using a compound having a tricyclodecane skeleton and/or a tricyclodecene skeleton and a sulfone group bonded thereto as a dispersant.