JPH0367556B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD OF THE INVENTION The present invention relates to solid fuel slurry compositions containing specific dispersants. Conventional technology Traditionally, an energy structure based on petroleum has been adopted, but due to the depletion of petroleum resources in recent years, coal,
Solid fuels such as petroleum coke and pituti are being rediscovered, and various ways to use 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, conventional methods for transporting these solid fuels include pulverizing the solid fuel and mixing it with water to form a water slurry composition, or adding a surfactant to such a water slurry composition to produce the solid fuel. Measures have been proposed to improve the dispersibility and stability of fluorophores in water. Problems 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, the slurry becomes unstable. This has problems such as impeding combustion efficiency and deteriorating combustion efficiency. 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 by employing a specific new dispersant, it is possible to give a slurry higher fluidity than conventional dispersants, and it can also last for a long time. An object of the present invention is to provide a solid fuel slurry composition that can maintain high fluidity even after being left for a long time. Means for Solving the Problems That is, the present invention provides (a) a norbornene derivative having 9 to 12 carbon atoms containing two double bonds in the molecule (however,
(excluding dicyclopentadiene and its derivatives)
and (b) a sulfonated product with a sulfonated double bond and/or a polymer thereof, and (b) a sulfonated product with a sulfonated double bond of a cyclohexene derivative having 8 to 12 carbon atoms and containing two double bonds in the molecule. The present invention provides a solid fuel slurry composition characterized in that solid fuel powder is dispersed in water using at least one selected from the group consisting of the following: and/or its polymer as a dispersant. The dispersant used in the present invention (a) is a norbornene derivative having 9 to 12 carbon atoms containing two double bonds in the molecule (excluding dicyclopentadiene and its derivatives). or (b) a sulfonated product or a polymer thereof, in which the double bond of a cyclohexene derivative having 8 to 12 carbon atoms containing two double bonds in the molecule is sulfonated. At least one type. The norbornene derivative used as the starting material for the dispersant (a) is a norbornene derivative with 9 to 12 carbon atoms that contains two double bonds in the molecule (however, the norbornene ring contains one double bond). can be,
It is usually represented by general formula (A) or (B). (In the formula, R ₁ and R ₂ are alkyl groups having 1 to 4 carbon atoms or hydrogen atoms, R ₃ and R ₄ are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and R ₅ is alkylene having 1 to 3 carbon atoms. group, R ₆ and R ₇ represent an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, R ₈ and R ₉ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and θ represents 0 or 1.) Note that the present invention In general formulas (A) and (B)

[expression] and

[Formula] is located at the 6th position, but may also be located at the 5th position. The norbornene derivatives represented by the above general formulas (A) and (B) can be produced by the Diers-Alder reaction with cyclopentadiene as the diene component and dienes excluding cyclodienes having 4 to 7 carbon atoms as the dienophile component, or by thermal decomposition of naphtha. It can be obtained by etc. Carbon number 4 or more used as dienophile component
Examples of the diene component in No. 7 are 1,3-butadiene, 1,2-butadiene, 1,2-pentadiene, 1,3-pentadiene, 2,3-pentadiene, isoprene, 1,2-hexadiene, 1,3
-hexadiene, 1,4-hexadiene, 1,5
-hexadiene, 2,3-hexadiene, 2,4
-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene,
1,2-heptadiene, 1,3-heptadiene,
1,4-heptadiene, 1,5-heptadiene,
1,6-heptadiene, 2,3-heptadiene,
2,5-heptadiene, 3,4-heptadiene,
These include 3,5-heptadiene and various branched dienes having 7 carbon atoms. When cyclopentadiene and the dienophile component are subjected to the Diels-Alder reaction, a norbornene derivative is produced in which double bonds other than the double bond of the norbornene ring having 9 to 12 carbon atoms and the double bond that acted as the dienophile remain. A typical example of this is 5-vinyl-
norbornene-2,5-ethylidene-norbornene-2,5-methylene-6-methylnorbornene-2,5-propenyl-norbornene-2,5-
Vinyl-6-methylnorbornene-2,5-isopropenyl-norbornene-2,5-methyl-5
-vinyl-norbornene-2,5-allyl-norbornene-2,5-vinyl-6ethylnorbornene-2,5-butenyl-norbornene-2, and the like. Next, the cyclohexene derivative used as the starting material for the dispersant (b) contains two double bonds in the molecule (however, there is one double bond in the cyclohexene ring).
It is a cyclohexene derivative having 8 to 12 carbon atoms, and is usually represented by the general formula (C), (D) or (E). (In general formulas (C), (D), and (E), R ₁₀ and R ₁₁ are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, R ₁₂ ,
R ₁₃ and R ₁₄ are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, R ₁₅ is alkylene groups having 1 to 4 carbon atoms,
R ₁₆ and R ₁₇ are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and θ is 0 or 1. ) In the present invention, in general formulas (C) and (D)

[expression] and

[Formula] is located at position 4, but may also be located at position 5. The cyclohexene derivative contains, as component (C),
Conjugated diene having 4 to 6 carbon atoms such as 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 2,3-dimethylbutadiene, as component (D), conjugated diene as component (C) Besides,
4 to 6 dienes such as 1,2-butadiene, 1,4-pentadiene, and cyclopentadiene,
This is a product obtained when component (C) is a diene and component (D) is a dienophile in a Diels-Alder reaction. Specific examples include 4-vinyl-cyclohexene, 1,4-vinylidene-cyclohexene-
1,4-ethylidene-cyclohexene-1,4-
Methylene-5-cyclohexene-1,4-isopropenyl-cyclohexene-1,4-isopropenyl-6-methyl-cyclohexene-1,4-propenyl-cyclohexene-1,4-propenyl-6-methyl-cyclohexene-1, 4-vinyl-5-methyl-cyclohexene-1,3-methyl-4-vinyl-cyclohexene-1,4-methyl-4-vinyl-cyclohexene-1,4-butenyl-cyclohexene-1, tetrahydroindene, 7-iso propenyl-cyclohexene-1,
1-Methyl-4-propenyl-cyclohexene-
1 etc. Methods for producing sulfonated products of these norbornene derivatives and cyclohexene derivatives and their polymers are described in Japanese Patent Application No. 139096/1983 and Japanese Patent Application No. 59-139096.
It is described in detail in the specification of No. 139097. Incidentally, to give an overview, in order to produce a sulfonated product of a norbornene derivative and/or a cyclohexene derivative (hereinafter, these derivatives may be simply referred to as "derivatives"),
Various methods can be considered, but for example, by preferentially adding sulfites to the highly reactive double bond among the two double bonds contained in the molecule of the derivative, Sulfonated derivatives containing one double bond can be obtained. As the sulfonating agent in this case, an alkali metal acid sulfite, metasulfite or sulfites are usually used alone or as a mixture. The amount of sulfonating agent per mole of derivative is:
Usually 0.1 to 2.0 mol, preferably 0.5 to 1.5 mol,
More preferably, it is 1 to 1.5 mol. If the amount is less than 0.1 mol, the reaction yield will be low, and if it exceeds 2.0 mol, a large amount of disulfonated product will be produced.
When the amount of the sulfonating agent is less than 1 mole per mole of the derivative, a mixture of the sulfonated derivative and the non-sulfonated derivative is formed. Only the sulfonated derivative (used) or distillation may be removed from the mixture, or a mixture of the sulfonated derivative and the non-sulfonated derivative may be directly polymerized by the method described below. In that case as well, the sulfonated polymer is
The non-sulfonated polymer can be separated by extraction (using e.g. n-hexane as solvent) or distillation. In the sulfonation reaction, the use of a catalyst is not necessarily required, but the use of a catalyst such as an inorganic oxidizing agent is usually effective in improving the yield and shortening the reaction time. Examples of the inorganic oxidizing agent include nitrates, nitrites, chlorates, etc., and nitrates are particularly effective. The amount of the inorganic oxidizing agent is not particularly limited, but 0.02 to 0.15 mol, preferably 0.05 to 0.1 mol is effective per mol of the derivative. Furthermore, in order to make the reaction proceed uniformly and smoothly,
Preferably, a suitable solvent is used. Examples of solvents that can be advantageously used include water, lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, and tertiary butyl alcohol, lower glycols, ketones,
Examples include ethers and esters. These solvents can be used in combination of two or more kinds as appropriate. Among these, a mixed solvent of lower alcohol and water, especially a mixed solvent of methyl alcohol and water, is recommended as an excellent solvent. The reaction temperature is usually 50 to 200°C, preferably 70°C.
It is carried out at a temperature of -150°C, more preferably 90 - 130°C, and can be carried out either at normal pressure or under elevated pressure. In order to suppress the progress of side reactions and reduce the production of inorganic salts, the pH of the reaction system is maintained at the usual range of 2 to 9, preferably 5 to 7. The cationic species of the sulfonated product is not particularly limited, but in order to make it water-soluble, hydrogen, alkali metals, alkaline earth metals, ammonium, amines and the like are preferred. Examples of the alkali metal include sodium and potassium, and examples of the amine include alkylamines such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, triethylamine, butylamine, dibutylamine, and tributylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, etc. Examples of alkaline earth metals include polyamines, morpholine, piperidine, etc., and calcium, magnesium, etc. as alkaline earth metals. These cationic species can also be interchanged with other cationic species by various ion exchange techniques. Next, the polymer of sulfonated derivatives in the present invention refers to a polymer obtained by polymerizing the same sulfonated derivatives, or a monomer that can be polymerized with the sulfonated derivatives (hereinafter referred to as It represents a polymer obtained by polymerizing a mixture with a comonomer (referred to as a "comonomer"). The method for producing this polymer is as follows. For example, a sulfonated product of the above derivative or a comonomer thereof is reacted in the presence of an acidic compound catalyst at a reaction temperature of usually -20 to 300°C, preferably 80°C.
A polymer can be produced by carrying out a polymerization reaction at ~180°C for several hours to several tens of hours. In the polymerization reaction, a solvent for the polymerization reaction can be used in order to carry out the reaction smoothly, and the solvent for the polymerization reaction may include polar solvents such as water, hydrocarbons, halogens, etc., as long as it does not hinder the polymerization reaction. Any suitable material such as carbonized hydrocarbons can be used. Examples of the acidic compound catalyst include Lewis acids such as sulfuric acid, phosphoric acid, hydrogen fluoride, boron trifluoride and its complexes, aluminum chloride, aluminum bromide, tin tetrachloride, zinc chloride, titanium trichloride, and organic protonic acids. be able to. Among them, sulfuric acid can be cited as a typical example. Comonomers include aliphatic, alicyclic, and aromatic hydrocarbons having olefinic double bonds, unsaturated amides, unsaturated alcohols, unsaturated esters, unsaturated nitriles, unsaturated carboxylic acids, and their like. Ester, unsaturated sulfonic acid and its ester, etc., aliphatic, alicyclic, aromatic alcohol or phenol, or alcohol or diol having an amino group, ester group, nitrile group, carboxylic acid group, sulfonic acid group, etc. 1 More than one species can be used in any proportion. By changing the type of comonomer used, the surface active properties of the polymer can be changed. When a polymer is produced from the sulfonated product of the present invention and a comonomer and used as a dispersant for solid fuel, the sulfonated product/polymer of the present invention (by weight) is used to suppress foaming. %) is 50% or more, preferably 70% or more. The molecular weight of the polymer and copolymer obtained by the present invention can be changed as appropriate by the reaction conditions, especially the type and amount of the acidic compound catalyst, the type and amount of the solvent, or the reaction temperature and reaction time. can. When using the polymers and copolymers obtained in this way as the dispersant of the present invention, the characteristics cannot be determined unambiguously because they vary depending on the type of solid fuel, particle size, etc., but usually The weight average molecular weight is preferably 500 or more, more preferably 1000 or more, and particularly preferably 2000 to 100000. In addition, sulfonated polymers and copolymers are
It can be mutually exchanged into acid form or salts of alkali metals, alkaline earth metals, ammonium, amines, etc. by ion exchange method or neutralization reaction. Next, the solid fuels used in the present invention are coal, petroleum coke, pitch, 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 . Pituchi 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, but lower than 50 °C. and is difficult to crush. Pitch contains almost no ash and moisture compared to coal, 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 is 70% by weight or more for 200 mesh passes, 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. One or more types of the dispersant of the present invention may be added to the solid fuel slurry at a concentration of 50 to 85% by weight, although not particularly limited, in combination with surfactants, additives, etc. described later as necessary. As the amount of the dispersant added increases, the viscosity of the slurry decreases, so the amount added can be selected according to the desired viscosity, and the amount added may be 0.01 to 10% by weight based on the total amount of the slurry composition.
From the viewpoint of workability and economy, the content is preferably 0.05 to 1% by weight. Surfactants that may be used as needed in the slurry composition of the present invention include nonionic surfactants, anionic surfactants, and the like. Examples of nonionic surfactants include alkyl polyether alcohols, alkylaryl polyether alcohols, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyalkylene oxide block copolymers. Commercially available products, such as those based on diethanolamines, diethanolamines, anhydrosorbitols, glycosides, gluconamides, glycerols, and glycidols, can be used as dispersants or particle wetting agents. Examples of the anionic surfactant include dodecylbenzene sulfonate, oleate, alkylbenzene sulfonate, dialkyl sulfosuccinate, lignin sulfonate, alcohol ethoxysulfate, secondary alkanesulfonate, and α-olefin sulfonate. , tamol, etc., and commercially available products such as carboxylic acid type, sulfuric acid ester type, sulfonic acid type, phosphoric acid ester type, and alkylaryl sulfonate type containing these can be used as dispersants or wetting agents. Examples of additives include chelating agents for trapping polyvalent metals contained in ash in solid fuels, potassium tetrapolyphosphate, sodium citrate, sodium gluconate, sodium polyacrylate, and polycarboxylic acids. Furthermore, an antifoaming agent may be added to suppress foaming. As the antifoaming agent, for example, silicone emulsion is used. Freezing point depressants can also be added to prevent freezing in winter. As the freezing point depressant, for example, a lower alcohol such as ethylene glycol or a polyhydric alcohol is used. The method for producing the slurry composition of the present invention is not particularly limited, and consists of mixing 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 the dispersant is added, or the solid fuel, water, and dispersant are added to a mill and the Any method can be used, such as mixing the fuel while pulverizing it. Effect When the dispersant of the present invention is present in the solid fuel slurry composition, the dispersant is adsorbed on the surface of the fuel particles, and the resulting electrostatic force and the relatively large steric hindrance of the dispersant itself prevent the particles from approaching each other. This results in reduced viscosity and stable dispersion of the composition. Examples Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that % in the examples is based on weight. Reference Examples 1 to 15 In a stainless steel autoclave 2 equipped with a stirring device and a thermometer, 2 moles of norbornene derivatives or cyclohexene derivatives shown in Table 1, 2 moles of sodium bisulfite (208 g), 0.4 moles of potassium nitrate (20 g), and methyl 500 ml of alcohol and 250 g of distilled water were charged, the container was sealed, and the reaction was carried out at a temperature of 130° C. for 5 hours while mixing under strong stirring.
Thereafter, after cooling to room temperature, the reaction mixture was taken out, 100 ml of distilled water and 300 ml of n-hexane were added, and mixed thoroughly. The separated n-hexane layer and the precipitate were removed, and the residue was concentrated and evaporated to dryness to form a pale yellow solid. was gotten. This solid was extracted with n-hexane for 1 hour using a Soxhlet extractor to remove unreacted substances,
After drying, the residual solution was dissolved in 500 ml of permanent acetic acid, and acetic acid-insoluble components such as inorganic salts were filtered off. The obtained acetic acid soluble portion was condensed to dryness to obtain a white-yellow solid. This solid was washed with ethanol and further dried to obtain the sodium salt of the sulfonate shown in Table 1. The results are shown in Table 1. Next, the following polymerization reaction was carried out using the sulfonated product. Charge 135 g of the above sulfonated product and 58 g of distilled water into a three-necked flask equipped with a stirrer and a thermometer, and after dissolving, add 98% sulfuric acid 135 while cooling the whole.
g was added dropwise over about 30 minutes with stirring, then heated in an oil bath, and polymerized over a period of 35 hours in the range of 110 to 125° C., taking samples along the way and checking the degree of polymerization by GPC. After polymerization, add 300 ml of distilled water to the reactor.
ml was added and dissolved, neutralized with calcium carbonate to remove the precipitate, sodated with sodium carbonate to obtain the sodium salt, and this solution was dried to give a second
A brown solid was obtained in the amount shown in the table.

【table】

[Table] Reference Examples 16 to 19 150 g of the sulfonated norbornene derivative obtained in Reference Example 1 and the compounds shown in Table 3 were charged and polymerized in the same manner as in Reference Example 1. 3rd result
Shown in the table.

[Table] Reference Examples 20 to 23 150 g of the sulfonated intermediate cyclohexene derivative obtained in Reference Example 8 and the compounds shown in Table 4 were each charged and polymerized in the same manner as in Reference Example 1. The results are shown in Table 4.

[Table] Examples 1 to 23, Comparative Examples 1 to 3 The coal used was Australian coal containing 76% 200 mesh coal, 6.5% ash, and 1.6% sulfur. Add the dispersant listed in Table 5 (0.5% of coal) into water, gradually add a predetermined amount of coal particles into the water, and mix at 3000 rpm with a homomixer.
A coal slurry with a concentration of 70% was prepared by stirring for 15 minutes. The viscosity of the coal slurry thus obtained was also measured at 25°C. The results are shown in Table 5. After that, the slurry was left to stand and its viscosity was measured over time to check its stability. In Table 5, the dispersants of Reference Examples 1 to 15 are all sodium salts of the corresponding polymers (second
(see table) (the same applies below). It can be seen from Table 5 that the coal slurry composition of the present invention is excellent.

【table】

[Table] Examples 24 to 29 A test was conducted at a slurry concentration of 70% according to Example 1 using domestically produced bituminous coal and anthracite coal of 73, 76 and 88%, respectively, for 200 mesh passes. The results are shown in Table 6.

[Table] Examples 30 to 40, Comparative Examples 4 to 6 Contains 70% of 200 mesh pass, ash content of 0.65%,
Petroleum coke containing 0.30% sulfur was used. The dispersant listed in Table 7 was added to water in advance, and a predetermined amount of petroleum coke was gradually added thereto, followed by stirring at 3000 rpm for 15 minutes using a homomixer to prepare a petroleum coke water slurry. Petroleum coke concentration is
The amount of 70% dispersant added was constant at 0.5% of petroleum coke. The viscosity of the slurry thus obtained was measured at 25°C and the results are shown in Table 7.
Furthermore, after the slurry was left to stand for 30 days, the viscosity of the slurry was also measured to examine its stability. It can be seen from Table 7 that the petroleum coke water slurry composition of the present invention is excellent.

【table】

[Table] Examples 41 to 45, Comparative Examples 7 to 9 Petroleum pitch with a softening point of 120°C was dry ground in a mill.
A fine powder of 73% was obtained after 200 mesh passes. The dispersant listed in Table 8 prepared in advance was dissolved in water, and the fine Pitch powder was added thereto and stirred at 3000 rpm for 15 minutes using a homomixer to obtain a slurry with a concentration of 70%. The amount of dispersant added was constant at 0.5% relative to pitch. The viscosity of the pitch slurry thus obtained was measured at 25°C. After that, the slurry was left to stand and the viscosity of the slurry was measured again 30 days later. The results are shown in Table 8, and it can be seen that both dispersibility and stability are extremely excellent.

【table】

[Table] *1 Naphthalene sulfonic acid condensate *2 Polyethylene oxide nonionic surfactant (HLB; 17.3)
Examples 46 to 47 Slurries were produced in the same manner as in Example 1 using the sodium salts of the sulfonates of Reference Examples 1 and 8 shown in Table 1. The results are shown in Table 9.

[Table] Effects of the Invention By selecting the specific dispersant as described above, the solid fuel slurry composition of the present invention can reduce the slurry viscosity compared to the conventional technology,
Therefore, the slurry has good viscosity dispersibility and fluidity, has little foaming property, and is suitable for transportation by pipeline.

Claims (1)

[Claims] 1 (a) Norbornene derivatives with 9 to 12 carbon atoms containing two double bonds in the molecule (excluding dicyclopentadiene and its derivatives) and/or their heavy (b) dispersion of at least one selected from sulfonated products of cyclohexene derivatives having 8 to 12 carbon atoms containing two double bonds in the molecule and/or polymers thereof; A solid fuel slurry composition characterized in that solid fuel powder is dispersed in water as an agent.