JPS62209198A - Solid fuel slurry composition - Google Patents

Abstract

PURPOSE:A weakly basic, highly concentrated solid fuel slurry composition keeping high fluidity even if it is allowed to stand for a long time, obtained by dispersing a solid fuel to water by the use of a sulfonated norbornene derivative as a dispersant. CONSTITUTION:A solid fuel is dispersed into water by the use of (A) a sulfonated norbornene derivative (polymer thereof) wherein double bonds of the 9-12C norbornene derivative containing two double bond in the molecule are sulfonated and/or (B) a sulfonated cyclohexene derivative (polymer thereof) wherein double bonds of the 8-12C cyclohexene derivative containing two double bonds in the molecule are sulfonated as a dispersant to give the aimed slurry composition of pH 7.2-9.

Description

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

[Conventional technology]

Traditionally, the energy structure has been based on petroleum, but in recent years, due to the depletion of petroleum resources, solid fuels such as coal, petroleum coke, and pitch have been rediscovered, and various ways of using 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, various techniques have been proposed in which solid fuel such as coal is pulverized and dispersed in water and treated as a slurry in the same way as a liquid.

In this case, it is possible to create a slurry with a low viscosity by lowering the solid fuel concentration and using a large amount of water, but this is not a good idea in terms of fuel efficiency. In addition, the slurry thus obtained has the disadvantage that the solid fuel settles when left standing.

As a method of increasing the solid fuel concentration, a method has been proposed in which various dispersants are added to the slurry to improve the dispersibility of the solid fuel in water. It has been reported that the fluidity of solid fuel slurries to which such various dispersants are added is significantly improved compared to when no such dispersants are added, and that the use of dispersants makes it possible to produce highly concentrated solid fuel slurries. There is.

[Problem that the invention seeks to solve]

Since the solid fuel slurry produced in this way is transported and stored in -a and used as a fuel, it is required that the slurry has good static stability over a long period of time.

However, the current situation is that long-term stability has not yet reached a fully satisfactory level.

An object of the present invention is to provide a solid fuel slurry composition that can impart high fluidity to a highly concentrated solid fuel slurry and maintain high fluidity even after being left for a long time. do.

[Means for solving problems]

As a result of intensive studies to solve the above-mentioned conventional technical problems, the present inventors have found that by adopting a specific new dispersant and adjusting the pH of the slurry, the amount of The present invention was achieved by discovering that a solid fuel slurry composition can be obtained that can give high fluidity to the slurry depending on the amount used and can maintain high fluidity even after being left for a long time. .

That is, the present invention provides (a) a sulfonated product and/or a polymer thereof in which the double bond of a norbornene derivative having 9 to 12 carbon atoms containing two double bonds in the molecule is sulfonated, and (b) a molecule thereof. A solid fuel is prepared by using a small amount (both of which are selected from sulfonated products and/or polymers thereof) of cyclohexene derivatives having 8 to 12 carbon atoms containing two double bonds as a dispersant. The present invention provides a solid fuel slurry composition that is dispersed in water and has a pH of 7.2 to 9.

The dispersant used in the present invention is (a) a sulfonated product of a norbornene derivative having 9 to 12 carbon atoms and having two double bonds in the molecule and/or a polymer thereof; (b1 is 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.

The norbornene derivative used as a starting material for a dispersant 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), and is usually , general formula (A), (B
) or a dicyclopentadiene derivative represented by (C).

R+ (wherein, R+-Rz is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, R,, R, is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R2 is an alkylene group having 1 to 3 carbon atoms, R4
, R7 is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, R
6, R7 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
θ represents O or 1. ) In the above general formulas (A) and (B), it is at position 6, but it may be at position 5.

The norbornene derivatives represented by the above general formulas (A), (B) and (C) are produced by the Diels-Alder reaction with cyclopentadiene as the diene component and with dienes having 4 to 7 carbon atoms, or with naphtha as the genophile component. Obtained by pyrolysis etc.

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, and cyclo. Pentadiene, 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, methylcyclopentadiene, ■.

2-Hebutadiene, 1.3-Hebutashev, l.

4-hebutadiene, 1,5-hebutadiene, 1゜6・-
In addition to hebutadiene, 2,3-hebutadiene, 2°5-hebutadiene, 3,4-hebutadiene, and 3°5-hebutadiene, they are various branched dienes having 4 to 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 genophile 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
Examples include -methyl-5-pinyrunorbornene-2,5-allyl-norbornene-2,5-vinyl-6ethylnorbornene-2,5-butenyl-norbornene-2 and dicyclopentadiene.

Next, the cyclohexene derivative used as the starting material for the other dispersant contains two double bonds in the molecule (however, the cyclohexene ring contains one double bond) and has 8 to 12 carbon atoms. is a cyclohexene derivative, and is usually represented by the general formula (D), (E) or (F).

(In general formulas (D), (E), (F), Rl 0%
R+ + is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R1□, RI3, and RI4 are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms;
3 is an alkyl group, Rls is an alkylene group having 1 to 4 carbon atoms, RI&, RI? is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and θ is O or 1. ) In the present invention, in general formulas (D) and (E), is at position 4, but may be at position 5.

The cyclohexene m8 compound contains 1,3 as the component (D).
-butadiene, 1,3-pentadiene, isoprene, 1
, 3-hexadiene, 2,3-dimethylbutadiene, etc., a conjugated diene having 4 to 6 carbon atoms, (E) as a component (D)
In addition to the 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 the component (D) and genophile as the component (E).

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-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-itubropenyl-cyclohexene-1,1-methyl-4-propenyl-cyclohexene-1, and the like.

These norbornene derivatives and cyclohexene m8
The method for producing the sulfonated product and its polymer is described in Japanese Patent Application No. 59-139,096 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, sulfonated derivatives containing one double bond in the molecule can be produced. Obtainable.

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.
．． The amount is 1 to 2.0 mol, preferably 0.5 to 1.5 mol, and more preferably 1 to 1.5 mol. If the amount is less than 0.1 mol, the reaction yield will be low (on the other hand, if it exceeds 2.0 mol, the production of disulfonated products will increase.If the amount of the sulfonating agent is less than 1 mol per 1 mol of the derivative, the sulfonation A mixture of the sulfonated derivative and the non-sulfonated derivative is produced; in that case, only the sulfonated derivative may be extracted from the mixture by extraction (using n-hexane, etc. as a solvent) or distillation; Alternatively, 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 is extracted (using n-hexane, etc. as a solvent). Alternatively, it can be separated from the non-sulfonated polymer 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 effectively 0.02 to 0.15 mol, preferably 0.05 to 0.1 mol, per 1 mol of the derivative.

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

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 50-200°C, preferably 70-200°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.

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

Next, the polymer of the sulfonated derivatives used in the present invention is a polymer obtained by polymerizing at least one of the sulfonated derivatives, or a polymer that can be polymerized with the sulfonated derivatives. It represents a polymer obtained by copolymerizing monomers (hereinafter referred to as "comonomers"). The method for producing this polymer is as follows.

For example, a sulfonated product of the above-mentioned derivative or a comonomer thereof is reacted 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 polymerization reaction solvent may be used to smoothly carry out the reaction,
As the solvent for the polymerization reaction, any solvent such as polar solvents such as water, hydrocarbons, halogenated hydrocarbons, etc. can be used as long as it does not interfere with the polymerization reaction.

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. 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. 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 copolymer used, the surfactant properties of the polymer can be varied.

When a polymer is produced from the sulfonated product of the present invention and a comonomer and used as a dispersant for solid fuel, in order to suppress foaming, the amount is preferably 50% by weight or more, and preferably 50% by weight or more. It is 70% by weight or more.

The molecular weight of the polymers and copolymers obtained by the present invention depends on the reaction conditions, especially the type and amount of the acidic compound catalyst, the type and amount of the solvent, or the reaction temperature.
It can be changed as appropriate depending on the reaction time.

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 The average molecular weight is preferably 500 or more, more preferably 1,000 or more, and particularly preferably 2,000 to 100,000.

Furthermore, 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, 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 obtained by distilling asphalt, pinch, etc., which are obtained as heavy residues from distillation during petroleum refining, by thermally decomposing them at higher temperatures to distill out cracked oil. Compared to coal, it is extremely difficult to get wet with water.

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 is 70% by weight or more of 200 mesospas, 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 is added to a solid fuel slurry having a concentration of 50 to 85% by weight, although not particularly limited, in combination with one or more surfactants, additives, etc. described later as necessary. Since the viscosity of the slurry decreases as the amount of the dispersant increases, the amount added can be selected depending on the desired viscosity, and is usually 0.01 to 10% of the total amount of the slurry composition.
% of the weight is sufficient, but from the viewpoint of workability and economy, it is set to 0.0.
5 to 1% by weight is preferred.

Surfactants that may be used as needed in the slurry composition of the present invention include nonionic and anionic surfactants.

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 glycoside, glycoside, gluconamide, glycerin, and glycidol can be used as dispersants or particle wetting agents.

Examples of anionic surfactants include dodecylbenzenesulfonate, oleate, alkylbenzenesulfonexysulfate, secondary alkanesulfonate, α-
Examples include olefin sulfonic acid and tamol, and commercially available products such as carboxylic acid, sulfuric ester, sulfonic acid, phosphoric ester, and alkylaryl sulfonate products containing these can be used as dispersants or wetting agents.

Examples of additives include chelating agents for trapping polyvalent metals contained 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.

Further, the amount of surfactant added as necessary to the present invention is not particularly limited as long as it is within an effective range, but is usually 0,001 to 2% by weight based on the solid fuel.
In particular, 0.01 to 1% by weight is preferable from the viewpoint of effectiveness and economy.

The slurry composition of the present invention is obtained by blending a specific dispersant into a solid fuel-water slurry composition as described above, but the composition is further made alkaline, preferably at a pH of 7.2. ~9, more preferably 7.5~8.8,
Particularly preferably, it is adjusted to 7.6 to 8.7.

When a slurry composition is produced using a solid fuel such as Pacific coal, Saxon Vale coal, or Middle Barb coal among solid fuels, the pH of the slurry becomes acidic, and the pH of the slurry becomes acidic.
Once adjusted, the viscosity of the slurry gradually decreases, and in some cases, when the pH exceeds 9, the viscosity of the slurry increases, not only eliminating the effect of alkalinity adjustment, but also causing the slurry composition to burn out. After doing so, it was found that the talent increased and this was not desirable.

Thus, if the slurry composition is acidic, the viscosity of the composition will increase, which is undesirable.

When the solid fuel slurry composition of the present invention is alkaline, particularly when its pH is in the range of 7.2 to 9, the dispersibility of the slurry composition is further improved, and a slurry composition with a low viscosity can be obtained with a low additive amount. It will be done.

The pH of the slurry composition in the present invention, such as adjustment to alkalinity, can be adjusted using an alkali. Such alkalis include sodium hydroxide,
Examples include ammonia, potassium hydroxide, calcium hydroxide, magnesium hydroxide, and the like.

If the slurry composition is highly alkaline, for example if its pH exceeds 9, adjust the pH by adding an organic acid such as acetic acid, acrylic acid, methacrylic acid, butyric acid, or an inorganic acid such as sulfuric acid or nitric acid. It is also possible to do so.

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, and adjusting the composition to be alkaline.

For example, solid fuel is dry-pulverized in advance and then mixed into an alkaline aqueous solution containing a dispersant, such as a sodium hydroxide aqueous solution; a slurry is made and then a predetermined amount of the dispersant and alkaline aqueous solution are added; Any method can be used, such as adding a predetermined amount of a solid fuel, a dispersant, and an alkaline aqueous solution to the mixture, and 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, and by adjusting the composition to be alkaline, the viscosity of the composition is further reduced and the dispersibility is stabilized.

〔Example〕

Hereinafter, the present invention will be explained in more detail by giving Examples.

In addition, in the examples, % is based on weight.

Reference Examples 1 to 4 2 moles of norbornene derivatives or cyclohexene derivatives shown in Table 1, 2 moles of sodium bisulfite (208 g), and 0.4 moles of potassium nitrate (20 g) were placed in a 21 stainless steel autoclave equipped with a stirring device and a thermometer.
), methyl alcohol 500mj! , add 250g of distilled water, close tightly and mix under strong stirring until the temperature reaches 130.
The reaction was allowed to proceed for 5 hours at °C. Thereafter, after cooling to room temperature, the reaction mixture was taken out and charged with 100 mA of distilled water and 300 mA of n-hexane! ! was added, mixed thoroughly and separated.
-The residue except the hexane layer and the precipitate was 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 a 1N Mitsuro flask equipped with a stirring device and a thermometer.
After melting, 135 g of 98% sulfuric acid was added dropwise over about 30 minutes while stirring while cooling the gold body, and then heated in an oil bath, taking samples along the way and checking the degree of polymerization with GPC in the range of 110 to 125 °C. 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 form the sodium salt. A brown solid was obtained in the amount shown in Table 2.

Table 1 Table 2 Reference Example 5 150 g of the sulfonated cyclopentadiene obtained in Reference Example 1 and 23 g of acrylic acid were charged and polymerized using the same recipe as in Reference Example 1. The results are shown in Table 3.

Table 3 Examples 1-7, Comparative Examples 1-4 Pacific coal slurry was prepared using the dispersants of Reference Examples 1-5 as follows.

First, 16 mesh passes of Pacific coal was used for 5 seconds, and a predetermined amount of coal, water, a dispersant, and sodium hydroxide for pH adjustment were placed in an 11-porcelain mill, and the mixture was rotated on a rotator for 20 hours.
A slurry with a 200 mesh bath content of 76±2% was prepared. The viscosity of the slurry thus obtained was measured using a B-type viscometer.

The results are shown in Table 4.

Example 8, Comparative Example 5 In Examples 1 to 7, middle barb coal was used instead of Pacific coal. The results are also shown in Table 4.

(The following is a blank space) Table 4 [Effects of the Invention] The solid fuel slurry composition of the present invention can be produced by using the above-mentioned specific sulfonated polymer as a dispersant and by adjusting the composition to be alkaline. It is possible to reduce the viscosity of the slurry compared to the technology of Suitable for transportation.

Claims (1)

[Claims] (1) (a) Number of carbon atoms containing two double bonds in the molecule: 9
A sulfonated product obtained by sulfonating the double bond of ~12 norbornene derivatives and/or a polymer thereof, and (
b) Solid fuel using 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 as a dispersant. A solid fuel slurry composition comprising a solid fuel slurry dispersed in water, the composition having a pH of 7.2 to 9.