JPS6197391A - Solid fuel slurry composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which retains high fluidity even when left at rest for a long time, prepd. by dispersing powdered solid fuel in water by use of a specified dispersant. CONSTITUTION:A dispersant consisting of a sulfonate of a polymer thereof is prepd. by sulfonqting the double bond of a 9-12C norbornene (derivative) having two double bonds in the molecule [excluding dicyclopentadiene (deriva tive)] shown by formula I or II (where R1,2 are 1-4C alkyl or H; R3,4 and R6-9 are H or 1-3C alkyl; R5 is 1.-3C alkylene; theta is 0 or 1) or by sulfonting the double bond of an 8-12C cyclohexene derivative having two double bonds in the moledule, shown by formula III-V (where R10,11 are H or 1-5C alkyl; R12-14 are H or 1-3C alkyl; R15 is 1-4C alkylene; R16,17 are H or 1-4C alkyl). The compsn. is obtained by adding 0.01-10 wt. % dispersant to a slurry prepd. by dispersing in wqter 50-85 wt. W powdered solid fuel in which particles passing through a 200-mesh sieve account for 70 wt. F or more.

Description

DETAILED DESCRIPTION OF THE INVENTION 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, petroleum coke,
Solid fuels such as pitch have been rediscovered, and various ways to use them are being considered.

However, unlike liquid fuels such as petroleum, these shaped fuels are solid, so it is difficult to transport them by ordinary pipelines, tank trucks, etc.

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

Problems to be Solved by the Invention However, in the former water slurry composition, when the solid fuel concentration is increased, the viscosity of the composition increases and the fluidity deteriorates, while when the concentration is decreased, the stabilization of the slurry is impaired. In addition, there are problems in that combustion efficiency is deteriorated.

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 problem, that is, the present invention is directed to (a) a dicyclopentyl derivative of norbornene derivatives having 9 to 12 carbon atoms (excluding dicyclopentadiene and derivatives thereof) containing two double bonds in the molecule; Sulfonated products with sulfonated heavy bonds and/or polymers thereof,
and (b) 8 carbon atoms containing two double bonds in the molecule.
A solid fuel slurry characterized in that solid fuel powder is dispersed in water using at least one selected from the group consisting of sulfonated double bonds of ~12 cyclohexene derivatives and/or polymers thereof as a dispersant. A composition is provided.

The dispersant used in the present invention is (a) 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 its polymer in which the double bond of a cyclohexene derivative having 8 to 12 carbon atoms containing two double bonds in the molecule is sulfonated. It is at least one kind selected from polymers.

Norbornene used as a starting material for dispersant (a) is a norbornene with 9 to 12 carbon atoms that contains two double bonds in the molecule (however, the norbornene ring contains one double bond). It is a derivative and usually has the general formula (A
) or (B).

(In the formula, R+, Rz are an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, R3, R, is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R3 is an alkylene group having 1.1 to 3 carbon atoms. , R6, R? represent an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, Rs and Rq represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and θ represents O or 1.) In the present invention, -i Although it is at the 6 position in formulas (A) and (B), it may be at the 5 position.

The norbornene mA'IQ form represented by the above general formulas (A) and (B) is produced by a Diels-Alder reaction with dienes excluding cyclopentadiene as the diene component and cyclodiene having 4 to 7 carbon atoms as the genophile component, Obtained by pyrolysis of naphtha.

Examples of diene components having 4 to 7 carbon atoms used as the genophile component include 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-hebutadiene, 1,3-hebutadiene, 114-hebutadiene, 1,5- heptadiene, 1,6-heptadiene,
2,3-hebutadiene, 2,5-hebutadiene, 3゜4
-heptadiene, 3,5-hebutadiene, and various branched dienes having 7 carbon atoms.

When cyclopentadiene and the Genophile component undergo a 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 gel fill remain.

Typical examples include 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 a starting material for the dispersant (b) is a cyclohexene derivative having 8 to 12 carbon atoms containing two double bonds in the molecule (however, the cyclohexene ring contains one double bond). It is a derivative and is usually represented by the general formula (C), (D) or (E).

RIa (in general formulas (C), (D), (E), R6°, R
11 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R1
□＋RI3. R14 is a hydrogen atom or has 1 carbon number
~3 alkyl group, RIS is an alkylene group having 1 to 4 carbon atoms, RI &+ Rl ? + is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and θ is O or l. ) In the present invention, although it is at position 4 in general formulas (C) and (D), it may be at position 5.

The cyclohexene derivative contains l, 3 as component (C).
-butadiene, 1,3-pentadiene, isoprene, 1
, 3-hexadiene, 2,3-dimethylbucudiene, etc., as component (D), (C
) component conjugated diene, 1,2-butadiene, 1.4
- It is a product obtained when 4 to 6 dienes such as pentadiene and cyclopentadiene are subjected to a Diels-Alder reaction with diene as component (C) and genophile as component (D).

To give a specific example, 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-14-propenyl-6-methyl-cyclohexene-1,4-vinyl-5-
Methyl-cyclohexene-1,3-J-f-4-vinyl-cyclohexene-1,4-methyl-4-vinyl-
Cyclohexene-1,4-butenyl-cyclohexene-
11 Tetrahydroindene, 7-ituprobenylcyclohexene-1. Examples include 1-methyl-4-propenyl-cyclohexene-1.

Sulfonating agents for these norbornene derivatives and cyclohexene derivatives and methods for producing their polymers are described in Japanese Patent Application No. 1982-139,096 and No. 59-139,0.
It is described in detail in the specification of No. 97.

Incidentally, to give an overview, various methods can be considered to produce sulfonated products of norbornene derivatives and/or cyclohexene derivatives (hereinafter, these derivatives may simply be referred to as "derivatives"). By preferentially adding sulfites to the highly reactive double bond among the two double bonds contained in the molecule of the λi form, a sulfone of a derivative containing one double bond in the molecule is obtained. can be obtained.

As the sulfonating agent in this case, acidic sulfites, metasulfites, or sulfites of alkali metals are usually used alone or as a mixture.

The amount of the sulfonating agent is usually 0 per mole of the derivative.
．． 1 to 2.0 mol, preferably 0. 5 to 1.5 moles,
More preferably, it is 1 to 1.5 mol.

If it 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 mA 4-isomer may be removed from the mixture by distillation (used) or by distillation, or a mixture of a sulfonated derivative and a non-sulfonated derivative may be directly polymerized by the method described below. In that case as well, the sulfonated polymer can be separated from the non-sulfonated polymer by extraction (using e.g. n-hexane as a solvent) or distillation.

Although the use of a catalyst is not necessarily required in the sulfonation reaction, the use of a catalyst such as an inorganic oxidizing agent is usually effective in improving the yield and shortening the reaction time. No JRt
Examples of i-forming agents include nitrates, nitrites, chlorates, etc., and nitrates are particularly effective.

Although the amount of the inorganic oxidizing agent is not particularly limited, it is effective to use an amount of 0.02 to 0.15 mol, preferably 0.05 to 0.1 mol, per 1 mol of the derivative.

Furthermore, it is preferable to use an appropriate solvent in order to allow the reaction to proceed uniformly and smoothly.

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, ethers, and esters. can be mentioned. Two or more of these solvents can be used in combination as appropriate. Among these, a mixed solvent of lower alcohol and water, especially a mixed solvent of methyl alcohol and water, is considered to be an excellent solvent.

The reaction temperature is usually 50 to 200°C, preferably 70 to 200°C.
It is carried out at 150°C, more preferably from 90 to 130°C, and can be carried out either at normal pressure or under increased pressure.

In order to suppress the progress of side reactions and reduce the production of inorganic salts, the pH of the reaction system is usually maintained at 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 described above. It represents a polymer obtained by polymerizing a mixture with a comonomer (hereinafter referred to as a "comonomer"). The method for producing this polymer is as follows.

For example, the sulfonated product of the derivative described above, or a comonomer thereof and a comonomer thereof, in the presence of an acidic compound catalyst, at a reaction temperature,
Usually, a polymer can be produced by carrying out a polymerization reaction at -20 to 300°C, preferably at 80 to 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 material such as carbonized hydrocarbons can be used.

As the acidic compound catalyst, Lewis acids such as sulfuric acid, phosphoric acid, hydrogen fluoride, boron trifluoride and its complexes, aluminum chloride, aluminum bromide, tin tetrahydride, zinc chloride, titanium trichloride, or organic protonic acids are used. can be mentioned.

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. esters, unsaturated sulfonic acids and their esters, aliphatic, alicyclic, aromatic alcohols or phenols, or alcohols or diols having amino groups, ester groups, nitrile groups, carboxylic acid groups, sulfonic acid groups, etc. 1 More than one species can be used in any proportion.

By varying the type of comonomer used, the surfactant properties of the polymer can be varied.

When producing a polymer from the sulfonated product of the present invention and a comonomer and using the polymer as a dispersant for solid fuel, in order to suppress foaming, the amount must be 50% or more, preferably 70%. That's all.

The molecular weights of the polymers and copolymers obtained by the present invention can be changed as appropriate by the reaction conditions, particularly the type and amount of the acidic compound catalyst, the type and amount of the solvent, or the reaction temperature and reaction time.

When the polymers and copolymers obtained in this way are used in the dispersant binding method 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 1,000 or more, and particularly preferably 2,000 to 100,000.

The sulfonated polymers and copolymers can be mutually exchanged into acid forms or salts of alkali metals, alkaline earth metals, ammonium, amines, etc. by ion exchange methods or neutralization reactions.

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

The coal may be lignite, sub-bituminous coal, bituminous coal, anthracite coal, etc., or may be coal obtained by cleaning these coals, and is not particularly limited.

Petroleum coke is residual coke produced by distilling asphalt, pinch, etc., which are obtained as heavy residues from distillation during petroleum refining, at higher temperatures and distilling cracked oil. 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. Pitch is a slurry with a high calorific value and contains almost no natural substance or moisture compared to coal! It can be made into a fee.

The particle size of these solid fuels may be any particle size as long as it is powder, since the Huai coal currently burned in thermal power plants has a content of 200 mesobus and 70% or more. This particle size serves as a rough guide. 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 solid fuel slurry at a concentration of 50-85% by weight. The larger the amount of dispersant added, the lower the viscosity of the slurry. Therefore, the amount added can be selected depending on the desired viscosity, and is usually 0.01 to 10% by weight based on the total amount of the slurry composition. 0.05 from the viewpoint of gender and economy
~1% by weight is preferred.

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. Use commercially available products such as chemistries, jetanolamines, anhydrosorbitols, glycosides, gluconamides, glycerin, and glycidol as dispersants or particles. W' Can be used as an IB agent.

Examples of anionic surfactants 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 fuel, 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 a freezing point depressant,
For example, lower alcohols such as ethylene glycol or polyhydric alcohols are 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; solid fuel, water, and a dispersant are added to a mill and the Any method can be used, such as mixing the fuel while pulverizing it.

When the dispersant of the present invention is present in the solid fuel slurry composition, the dispersant is adsorbed onto 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. As a result, the viscosity of the composition is reduced and stable dispersibility is 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.

Reference Examples 1 to 15 2 moles of the norbornene derivative or cyclohexene derivative shown in Table 1 and 2 moles of sodium hydrogen sulfite were placed in a stainless steel autoclave equipped with a stirring device and a thermometer.
mole (208g), potassium nitrate 0.4 mole (20g)
, 500 ml of methyl alcohol and 250 g of distilled water, sealed and mixed under strong stirring at a temperature of 130°C.
The reaction was carried out for 5 hours. Then, after cooling to room temperature,
Take out the reaction mixture and 100ml of distilled water! Then, 300 ml of n-hexane was added and thoroughly mixed. The separated n-hexane layer and the residue except for the precipitate were concentrated and evaporated to dryness to obtain a pale yellow solid. This solid was extracted with n-hexane for 1 hour using a Soxhlet extractor to remove unreacted substances, and the remaining liquid was dried and dissolved in 500 mff of glacial 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.

Equipped with a stirring device and thermometer 17! 135 g of the above-mentioned sulfonated product and 58 g of distilled water were placed in a three-ring flask.
After melting, 135 g of 98% sulfuric acid was added dropwise over about 30 minutes while cooling the gold body, followed by heating it in an oil bath, and heating it in the range of 110 to 125°C while checking the degree of polymerization with GPC, with sampling midway through. Polymerization took place for 35 hours.

After the polymerization, 300 ml of distilled water was added to the reactor to dissolve it, neutralized with calcium carbonate to remove the precipitate, and then soap-jooned with sodium carbonate to make the sodium salt. This solution was dried and shown in Table 2. The indicated amount of brown solid was obtained.

Table 1 Table 2 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 each charged and polymerized using the same recipe as in Reference Example 1. The results are shown in Table 3.

Table 3 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 using the same recipe as Reference Example 1. The results are shown in Table 4.

Table 4 Examples 1 to 23, Comparative Examples 1 to 3 Coal was produced in Australia and 7
6%, 6.5% ash, and 1.6% sulfur were used. 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 stir for 15 minutes at 3.00 rpm using a homomixer to determine the concentration. A 70% coal slurry was prepared.

In addition, the viscosity of the coal slurry obtained in this way was 25
Measured at °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 sodium salts of the corresponding polymers (see Table 2) were used as the dispersants in Reference Examples 1 to 15 (see Table 2 below).

It can be seen from Table 5 that the coal slurry composition of the present invention is excellent.

Table 5: 16.3 (HLB; 16.3) Examples 24 to 29 Example 1 using domestically produced bituminous coal, sub-bituminous coal, and anthracite with a content of 73.76% and 88%, respectively.
The test was conducted at a slurry concentration of 70% in accordance with . The results are shown in Table 6.

Table 6 Examples 30 to 40, Comparative Examples 4 to 6 Contains 70% of 200 mesh pass, ash content 0.65%
, petroleum coke containing 0.30% sulfur was used. Pour the dispersant listed in Table 7 into water, gradually add a predetermined amount of petroleum coke, and mix with a homomixer for 30 minutes.
．． A petroleum coke water slurry was prepared by stirring at 00 rpm 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 viscosity of the slurry thus obtained was measured at 25°C and the results are shown in Table 7. Further, after the slurry was left to stand for 30 days, the viscosity of the slurry was also measured to examine its stability.

Table 7 shows that the petroleum coke water slurry composition of the present invention is superior.

Table 7 Examples 41 to 45, Comparative Examples 7 to 9 Petroleum pitch with a softening point of 120°C was dry ground in a mill and
A fine powder with a mesophyll content of 73% was obtained.

Dissolve the dispersant listed in Table 8 prepared in advance in water, add the pinch fine powder in it, and mix with a homomixer to 3.0
The mixture was stirred at 0 rpm for 15 minutes to obtain a slurry with a concentration of 70%.

The amount of dispersant added was constant at 0.5% relative to the pitch.

The viscosity of the pitch slurry thus obtained was determined at 25°C.
Measured at 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 the dispersibility and stability are extremely excellent.

Table 8 Examples 46 to 47 Slurries were produced in the same manner as in Example I 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 9 Effects of the Invention The solid fuel slurry composition of the present invention can lower the slurry viscosity compared to the conventional technology by selecting the specific dispersant as described above, and therefore has a good dispersibility of the slurry viscosity. It has good fluidity and low foaming properties, making it suitable for transportation by pipeline.

Claims (1)

[Claims] 1, (a) 9 or more carbon atoms containing two double bonds in the molecule
12 norbornene derivatives (however, excluding dicyclopentadiene and its derivatives), sulfonated products with sulfonated double bonds and/or polymers thereof, and (b
) At least one selected from the group consisting of sulfonated double bonds of cyclohexene derivatives having 8 to 12 carbon atoms containing two double bonds in the molecule and/or polymers thereof is used as a dispersant to produce solid fuel. A solid fuel slurry composition comprising powder dispersed in water.