JPS6248795A - Solid fuel slurry composition - Google Patents

Abstract

PURPOSE:A solid fuel slurry composition, containing specific sulfonated aliphatic diene and/or a polymer thereof as a dispersing agent and capable of keeping high fluidity even on allowing to stand for a long time. CONSTITUTION:A solid fuel slurry composition obtained by adding normally 0.01-10wt% preferably 0.05-1wt% sulfonated 4-7C aliphatic diene, e.g. 1,3- pentadiene, isoprene, 1,4-hexadiene, 1,3-pentadiene/dicyclopentadiene (at 3/7 molar ratio) and/or polymer thereof as a dispersing agent thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a solid fuel slurry composition containing a specific dispersant.

[Conventional technology]

Traditionally, the energy structure has been based on petroleum, 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 solid fuels are solid and therefore difficult to transport by ordinary pipelines, tank trucks, and the like.

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.

[Problem that the invention seeks to solve]

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, stabilization of the slurry is hindered and combustion efficiency is deteriorated. There are problems such as:

Furthermore, even in the latter water slurry composition containing a surfactant, the dispersibility and stability of the slurry over time 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 problems]

That is, the present invention provides a solid fuel slurry composition characterized in that solid fuel powder is dispersed in water using a sulfonated product of an aliphatic diene having 4 to 7 carbon atoms and/or a polymer thereof as a dispersant. It is something.

Examples of aliphatic dienes having 4 to 7 carbon atoms (hereinafter sometimes referred to as "aliphatic dienes") containing two double bonds in the molecule used in the present invention include 1,3-butadiene, l, 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, 1.4 -heftadiene, ■, 5-hebutadiene, 1
．． 6-heptadiene, 2,3-hebutadiene, 2,5-
Examples include hebutadiene, 3,4-hephtadiene, 3,5-heptadiene, and various branched dienes having 4 to 7 carbon atoms.

These aliphatic dienes can be used alone or in combination of two or more.

Further, in the present invention, a compound having a tricyclodecane skeleton or a tricyclodecene skeleton can also be used in combination with the aliphatic diene.

A typical example of a compound having such a tricyclodecane skeleton or tricyclodecene skeleton is dicyclopentadiene (hereinafter, these compounds may be referred to as "dicyclopentagenes"). The skeleton is shown as (a) and (b) below.

(That is, tricyclo(5,2,1,02.6)decane or decene) Specific examples of such dicyclopentadiene include dicyclopentadiene, dimethyldicyclopentadiene, and the like.

These compounds can be used alone or in combination of two or more.

Moreover, when dicyclopentadines are used together with aliphatic dienes, a molar ratio of aliphatic dienes/dicyclopemetadienes (molar ratio) of -10 to 100/90 to 0 is usually preferred.

Various methods can be considered to produce sulfonated products of aliphatic dienes or dicyclopentadines, but
For example, it can be produced by sulfonating the double bond of these aliphatic dienes or dicyclopentadines by the method shown below.

That is, the sulfonation reaction applied to unsaturated compounds, especially unsaturated aliphatic or unsaturated alicyclic compounds, is described in Gilbert's book [Sulfonation and Related Reactions J (5 sulfonation and Reactions J)].
lated Reactjon”), Interscience Publications Inc.
jersey publishers in
(1965), and Charles J.
Norton et al., The Journal of Organic Chemistry
Sulfonation can also be carried out by the addition reaction of sulfites to unsaturated bonds, as shown in the study in Organic Chemistry, p. 4158 (1968).

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 generally 0.1 to 4 mol, preferably 0.5 to 2 mol, more preferably 1 to 1.
It is 5 moles.

If it is less than 0.1 mol, the reaction yield will be low, while if it exceeds 4 mol, a large amount of disulfonated product will be formed.

If the amount of sulfonating agent is less than 1 mol per mol of aliphatic diene or dicyclopentadiene, a mixture of sulfonated and non-sulfonated substances will be formed; As a solvent, for example, n-
Only the sulfonated product may be removed from the mixture by distillation (using hexane, etc.), or a mixture of the sulfonated product and the non-sulfonated product may be directly (co)polymerized by the method described below.

In that case as well, the sulfonated (co)polymer is extracted (
The non-sulfonated (co)polymer can be separated from the non-sulfonated (co)polymer using, for example, n-hexane as a solvent) or by 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.

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 is 0.02 to 0.15 mol, preferably 0.05 to 0.15 mol, preferably 0.05 to 0.15 mol, per 1 mol of aliphatic diene or dicyclopentadiene.
, 1 mole is effective.

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 recommended as 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 obtained is not particularly limited, but in order to make it water-soluble, hydrogen,
Preferred are alkali metals, alkaline earth metals, ammonium, amines, and the like.

The alkali metals include sodium, potassium, etc., and the amines include alkylamines such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, etc. Examples of the alkaline earth metal include polyamine, morpholine, piperidine, etc., and calcium, magnesium, etc.

Additionally, these cationic species can be interchanged with other cationic species by various ion exchange techniques.

Next, the (co)polymer of the sulfonated aliphatic dienes (and the sulfonated dicyclopentadines) used in the present invention refers to at least one of the sulfonated aliphatic dienes. A polymer obtained by polymerizing seeds, or a random type obtained by copolymerizing a sulfonated product of the aliphatic diene and a sulfonated dicyclopentadiene when dicyclopentadines are used together. It is a copolymer of

The method for producing such a (co)polymer is as follows.

For example, the sulfonated products of aliphatic dienes (and the sulfonated products of dicyclopentadiene) are reacted in the presence of an acidic compound catalyst at a reaction temperature of usually -20 to 300°C, preferably 80 to 180'C for several hours. A (co)polymer can be produced by carrying out a polymerization reaction for several tens of hours.

In the above (co)polymerization reaction, a polymerization reaction solvent can be used to smoothly carry out the reaction, and such a polymerization reaction solvent may include a polar solvent such as water, or carbonization as long as it does not interfere with the (co)polymerization reaction. Any hydrogens, halogenated hydrocarbons, etc. 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.

In the present invention, when a sulfonated aliphatic diene and a sulfonated dicyclopentadiene are copolymerized to obtain a copolymer, the copolymerization ratio of the two is determined by the mixed use of the sulfonated products. Similarly, it is preferable that the sulfonated product of aliphatic dienes/sulfonated product of dicyclopentadiene (molar ratio) = 10-1oo/90-0.

That is, it is preferable that the aliphatic diene content is 10 mol % or more in terms of the dispersibility of the resulting composition.

Further, when (co)polymerizing these sulfonated aliphatic dienes (and sulfonated dicyclopentadines), it is also possible to copolymerize other comonomers.

Such copolymerization! [The bodies include aliphatic, alicyclic, and aromatic hydrocarbons with olefinic double bonds, unsaturated amines, unsaturated alcohols, unsaturated esters, unsaturated nitriles, unsaturated carboxylic acids and their esters, and unsaturated nitrites. One or more types of saturated sulfonic acids and esters thereof, aliphatic, alicyclic, aromatic alcohols or phenols, or alcohols or diols having amino groups, ester groups, nitrile groups, carboxylic acid groups, sulfonic groups, etc. It can be used at a ratio of

In particular, from the standpoint of dispersibility, those copolymerized with unsaturated carboxylic acids such as acrylic acid and methacrylic acid are preferred.

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

In this case, when a copolymer is produced from the sulfonated product of the present invention and a comonomer and the copolymer is used as a dispersant for solid fuel, in order to suppress foaming, 50% by weight or more is required. , preferably 70% by weight or more, more preferably 90% by weight or more.

The molecular weight of the (co)polymer 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.

The weight average molecular weight of the (co)polymer used in the present invention obtained in this way before forming a salt depends on the reaction conditions, especially the type and amount of the acidic compound catalyst, and the type and amount of the solvent. Alternatively, the reaction temperature and reaction time can be changed as appropriate.

For example, when a (co)polymer is used as a dispersant for solid fuel, it cannot be determined unambiguously because the properties vary depending on the type of solid fuel, particle size, etc., but usually the weight average molecular weight is 500 or more. It is preferably 1,000 or more, more preferably 2,000 to 100,
000 is particularly preferred.

The (co)polymer used in the present invention can be mutually exchanged into an acid form or a salt of an alkali metal, alkaline earth metal, ammonium, amine, etc. by an ion exchange method or a neutralization reaction.

In addition, the (co)polymer obtained in this way can be obtained by:
The water-soluble ((
A salt of the co)polymer is obtained.

The cationic species for forming a salt on the sulfonic groups of the (co)polymer used in the present invention, that is, the cationic species of the sulfonated product, are not particularly limited. , alkali metals, alkaline earth metals,
Ammonium, amines, etc. 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.

Additionally, these cationic species can be interchanged with other cationic species by various ion exchange techniques.

In this way, an aqueous solution of the water-soluble (co)polymer salt is prepared, but in the present invention, if necessary, these salts are separated from the aqueous solution and dried to obtain a solid water-soluble (co)polymer salt. I can do it.

The water-soluble (co)polymer of the present invention can be mutually exchanged into an acid form or a salt such as an amine by an ion exchange method or a neutralization reaction.

Further, the degree of neutralization of the sulfonic groups may be appropriately selected within a range that makes the (co)polymer salt water-soluble or water-dispersible, and furthermore, the sulfonic groups may form different salts. .

The structure of the sulfonated compound or its polymer (salt) used in the present invention can be confirmed from the absorption of sulfonic groups by infrared absorption spectrum, and the composition ratio of these can be determined by acid/alkali titration such as potential difference and conductivity. You can know.

Furthermore, the structure can be confirmed by the presence of dicyclopenkune rings and the like using nuclear magnetic resonance spectroscopy.

Methods for producing these sulfonated dienes and their polymers are described in Japanese Patent Application No. 139,096/1986,
9-139,097 in detail.

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 coal, etc., or may be coal obtained by cleaning these coals, and is not particularly limited.

Petroleum coke is residual coke that is obtained by thermally decomposing 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 .

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. Compared to coal, pitch contains almost no ash and moisture 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 has a 200 mesobus content of 70% by weight or more, 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.

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.

Since the viscosity of the slurry decreases as the amount of the dispersant increases, the amount to be added can be selected depending on the desired viscosity, and is usually 0.01 to IO% relative to the total amount of the slurry composition. 0.05~ from the viewpoint of workability 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. Commercially available products, such as those based on fluorophores, jetanolamines, anhydrosorbitols, glycosides, gluconamides, glycerin, and glycidol, can be used as dispersants or particle wetting agents.

Examples of anionic surfactants include dodecylhenzenesulfonate, oleate, alkylbenzenesulfonate, dialkylsulfosuccinate, lignosulfonate, alcohol ethoxysulfate, secondary alkanesulfonate, and α-olefin sulfonate. Commercially available products such as carboxylic acid, sulfuric ester, sulfonic acid, phosphoric ester, and alkyl sulfonate containing acids and tamol 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.

Moreover, an antifoaming agent can also 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 solid fuel, water, and a dispersant are added to a container. Any method can be implemented, such as a method of 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 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.

〔Example〕

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 5 Equipped with a stirring device and a thermometer 2! ! 2 moles of aliphatic dienes (and dicyclopentadines) shown in Table 1, 2 moles of sodium bisulfite (208 g), and 0.4 moles of potassium nitrate (20 g) in a stainless steel autoclave.
), methyl alcohol 500mj2, distilled water 250g
and while mixing under strong stirring, heat the mixture to 13°C.
The reaction was allowed to proceed for 5 hours at 0°C.

After that, after cooling to room temperature, take out the reaction mixture and add 1 ml of distilled water.
00mj! Then, 300 ml of n-hexane was added thereto 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 then extracted with glacial acetic acid.
00 ml, 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.

135 g of the above sulfonated product and 58 g of distilled water were charged into 12 three-necked flasks equipped with a stirring device and a thermometer.
After dissolving, while cooling the gold body, 135 g of 98% sulfuric acid was added dropwise with stirring over about 30 minutes, then heated in an oil bath, sampling was carried out midway through, and the degree of polymerization was determined by gel permeation chromatography (GPC). 110 while checking
Polymerization was carried out for 35 hours in the range of ~125°C.

After the polymerization, 300 ml of distilled water was added to the reactor to dissolve it, neutralized with lucilleum carbonate to remove the precipitate, soap-jooned with sodium carbonate to form a sodium salt, and the solution was dried to give the results shown in Table 2. A brown solid was obtained in the amount indicated in .

Table 1 Table 2 Reference Examples 6 to 9 150 g of the sulfonated norbornene derivative obtained in Reference Example 1 and the compounds shown in Table 3 were each charged, and Reference Example 1 was prepared.
Polymerization was carried out using the same recipe.

The results are shown in Table 3.

Examples 1 to 9, Comparative Examples 1 to 3 Coal was produced in Australia and was used for 7 min.
6%, ash content of 6.5%, and sulfur content of 1.6%.

Add the dispersant listed in Table 4 to the water (0.5% based on coal).
), a predetermined amount of coal particles were gradually added therein, and the mixture was stirred for 15 minutes at 3.00 Orpm using a homomixer to prepare a coal slurry with a concentration of 70%.

In addition, the viscosity of the coal slurry obtained in this way was
Measured at 5″C.

The results are shown in Table 4.

After that, the slurry was left to stand and its viscosity was measured over time to check its stability.

In addition, in Table 4, the sodium salt of the corresponding polymer (see Table 2) was used as the dispersant in Reference Examples 1 to 5 (the same applies hereinafter).

It can be seen from Table 4 that the coal slurry composition of the present invention is excellent.

Examples 10 to 13, Comparative Examples 4 to 6 Contains 70% of 200 barley powder, and ash content is 0.65%
, petroleum coke containing 0.30% sulfur was used.

A dispersant listed in Table 4 was added to water in advance, and a predetermined amount of petroleum coke was gradually added thereto, followed by stirring for 15 minutes at 3.00 Orpm using a homomixer to prepare a petroleum coke water slurry.

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 4.

Furthermore, after the slurry was left to stand for 30 days, the viscosity of the slurry was also measured to examine its stability.

Table 4 shows that the petroleum coke water slurry composition of the present invention is excellent.

Table 4 *l) Condensate of naphthalene sulfonic acid *2) Polyethylene oxide nonionic surfactant (
HLB; l 6.3) Examples 14 to 17, 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 mesh pass content of 73% was obtained.

Dissolve the dispersant listed in Table 5 previously obtained in water, add the fine pitch powder therein, and mix with a homomixer in 3. O
The mixture was stirred at OOrpm 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 5, and it can be seen that both dispersibility and stability are extremely excellent.

Table 5 *1) Naphthalene sulfonic acid condensate *2) Polyethylene oxide nonionic surfactant (
HLB i 17.3) [Effects of the Invention] By selecting the specific dispersant as described above, the solid fuel slurry composition of the present invention can lower the slurry viscosity compared to the conventional technology. The slurry has good dispersibility and fluidity, and has low foaming properties, making it suitable for transportation by pipeline.

Claims (1)

[Claims] (1) A solid fuel slurry composition characterized in that solid fuel powder is dispersed in water using a sulfonated aliphatic diene having 4 to 7 carbon atoms and/or a polymer thereof as a dispersant.