JPS6335691A - Dispersant for water slurry of finely divided carbonaceous material - Google Patents

Abstract

PURPOSE:To provide the title dispersant capable of providing a highly concentrated water slurry of a finely divided carbonaceous material exhibiting excellent long-term stationary stability, which comprises an alkaline earth metal salt of a particular polymer, a polyether compound (or its derivative), and a sulfonation product (an alkaline earth metal salt thereof). CONSTITUTION:20-90wt% alkali metal salt of a sulfo group-contg. arom. hydrocarbon polymer selected from among a polymer (a) obtd. by polymerizing a polymerizable arom. sulfonic acid monomer (i) with a polymerizable hydrocarbon monomer (ii), if necessary, and a polymer (b) obtd. by polymerizing component (ii) to prepare a polymer having a polymerizable arom. monomer and then sulfonating the polymerizable arom. monomer, or an alkali metal salt, an ammonium salt or an org. amine salt thereof (A) is blended with 1-60wt% polyether compd. (or its derivative) (B) having an MW of 500-5,000 and comprising a compd. having an arom. ring and an active hydrogen and an ethylene oxide-contg. alkylene oxide and 1-60wt% sulfonation product (C) selected from among ligninsulfonic acid, a condensate of formaldehyde with a sulfo group-contg. arom. compd., and a condensate of formaldehyde with a sulfo group-contg. aminotriazine compd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dispersant used in an aqueous slurry of carbonaceous fine powder, such as coal or petroleum coke.

From the perspective of soaring oil prices and the diversification of energy resources,
Coal 1, whose use has been drawing attention in recent years, is a solid fuel and has shortcomings in terms of handling, so it has been proposed to pulverize it into a water slurry. By turning solid fuels such as coal or petroleum coke into a water slurry, it becomes possible to transport them through pipes and handle them in the same way as liquid fuels, but in order to improve transport efficiency, it is necessary to increase the concentration. . However, it is difficult to obtain a slurry with a high concentration of 50% or more by simply dispersing fine carbonaceous powder such as coal or petroleum coke in water.
Furthermore, if left standing, the carbonaceous fine powder will settle and become non-uniform, which poses a problem in terms of storage stability.

Therefore, it has been proposed to add a dispersion stabilizer to the slurry to increase the concentration and improve the dispersion stability.

Such dispersants include, for example, naphthalene sulfonic acid formalin condensate (Japanese Patent Application Laid-Open No. 56-21636), a two-component system of polyether added with ethylene oxide and styrene sulfonic acid/styrene copolymer salt (specially JP-A No. 60-250096), two-component system of polyether added with ethylene oxide and polystyrene sulfonate (JP-A No. 60-250097), aliphatic aldehyde addition condensates of naphthalene sulfonated products or salts thereof, etc. and a two-component system of polystyrene sulfonate or styrene/styrene sulfonate copolymer (JP-A-60-250094), an aliphatic aldehyde addition condensate of polyether added with ethylene oxide and naphthalene sulfonate, or A three-component system of its salt, etc., and a polystyrene sulfonate or a styrene/styrene sulfonate copolymer (Japanese Patent Application Laid-Open No. 60-252694)
etc. have been reported.

However, although these conventional dispersants have been shown to have a corresponding effect, they are still insufficient both in increasing the concentration of the slurry and in terms of static stability, and further improvements are still needed.

On the other hand, when focusing on the combustion of a water slurry of carbonaceous fine powder, the performance required of a dispersant is to reduce the water content in the water slurry, that is, increase the carbonaceous concentration, in order to improve combustion efficiency. However, at the same time, it is also important to minimize adverse effects on other combustion characteristics. However, many of the conventional anionic dispersants mentioned above are alkali metal salts such as sodium salts and potassium salts, and when a water slurry of carbonaceous fine powder using these is combusted, the melting point of the ash content is lowered. It has been desired to reduce the amount of alkali metals, because the molten material adheres to the heating surfaces and reheaters inside the boiler and solidifies and accumulates as it cools, increasing slagging and fouling.

Purpose of the Invention The present invention provides that when added to an aqueous slurry of carbonaceous fine powder,
It has excellent properties of lowering the viscosity of the slurry and improving its fluidity, making it possible to achieve higher concentrations, as well as providing long-term stationary stability.

The present invention provides a dispersant that can suppress increases in slagging and fouling.

The dispersant for water slurry of carbonaceous fine powder of the present invention is characterized by containing the following components (A), (B) and (C).

(A): An alkaline earth metal salt of one or more sulfonic acid group-containing aromatic hydrocarbon polymers selected from the following polymers (A1) and (A2).

(A1) A polymer obtained by polymerizing one or more monomers selected from (a) a polymerizable aromatic sulfonic acid monomer group and (b) a polymerizable hydrocarbon monomer group. A polymer containing the above-mentioned group (a) monomer as an essential component.

(A2) A polymer obtained by polymerizing one or more monomers selected from the group of polymerizable hydrocarbon monomers, which contains at least one polymerizable aromatic monomer.
A polymer obtained by sulfonating a polymer containing as an essential component of seeds.

(B) A polyether compound or a derivative thereof obtained by adding an alkylene oxide containing ethylene oxide as an essential component to a compound having an aromatic ring and active hydrogen in two molecules.

(C): At least one sulfonated product selected from the following (C1), (C2) and (C3) or an alkaline earth metal salt thereof (C1): Lignosulfonic acid or an alkaline earth metal salt thereof (C2) Sulfone Formaldehyde condensate of acid group-containing aromatic compound or alkaline earth metal salt thereof (C3) Formaldehyde condensate of sulfonic acid group-containing aminotriazine compound or alkaline earth metal salt thereof The polymer of component (A) of the present invention is: It contains an aromatic hydrocarbon containing a sulfonic acid group in the molecule as a constituent unit. The polymer (A1) is one in which the sulfonic acid group is derived from a monomer, that is, a polymer obtained by polymerizing an aromatic hydrocarbon monomer containing a sulfonic acid group alone or together with other monomers. On the other hand, the polymer (A2) is obtained by polymerizing monomers to obtain a polymer and then introducing sulfonic acid groups into the aromatic groups in one polymer.

The polymer (A1) is a polymer composed of one or more monomers selected from the following groups (a) and (b), and includes at least a structural unit derived from the monomers of group (a). It includes.

(a) Polymerizable aromatic sulfonic acid monomer (b) Polymerizable hydrocarbon polymer The proportion of the aromatic sulfonic acid monomer of group (a) in the (8") polymer is 40 to 100. mol% is preferred, more preferably 50 to 100 mol%.In this way, without using monomers of group (b), (a)
The polymer (A1) can also be constituted by only the aromatic sulfonic acid monomers of the group.

Specific examples of group (a) monomers include styrene sulfonic acid, α-methylstyrene sulfonic acid, vinyltoluenesulfonic acid, and vinylnaphthalenesulfonic acid.

Specific examples of group (b) monomers include styrene, α-methylstyrene, vinyltoluene, ethylene, butene, butadiene, diisobutylene, cyclopentadiene, and dicyclopentadiene.

Copolymers of group (a) monomers and group (b) monomers include styrene sulfonic acid/styrene copolymer, styrene sulfonic acid/butadiene copolymer, styrene sulfonic acid/butene copolymer, and α-methylstyrene. Sulfonic acid·
Examples include ethylene copolymer and α-methylstyrene sulfonic acid/diisobutylene copolymer.

The polymer (A2) is a sulfonated product of at least one type of hydrocarbon monomer, which contains at least one aromatic monomer as an essential component;
Or its salt.

Examples of aromatic monomers include styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, and indene. Examples of non-aromatic hydrocarbon monomers include ethylene, butene, butadiene, and dichloromethane. Examples include isobutylene, cyclopentadiene, and dicyclopentadiene. The proportion of aromatic monomers in the polymer of these monomers is suitably 30 to 100 mol%, preferably 50 to 100 mol%.

Specific examples of this polymer include polystyrene, styrene/ethylene copolymer, styrene/diisobutylene copolymer, styrene/dicyclopentadiene copolymer, and styrene/vinyltoluene/α-methylstyrene/indene copolymer. Petroleum resins such as By sulfonating such a polymer and further converting it into a salt (A2)
A polymer of For sulfonation, use sulfuric anhydride.

This can be carried out by applying any sulfonation method using a sulfonating agent such as chlorosulfonic acid or a sulfuric anhydride/Lewis base complex.

The weight average molecular weight of the sulfonic acid group-containing aromatic hydrogen polymer as component (A) is preferably 1,000 to 200,000.

The polymer (A1) or (80) of the present invention can use a crosslinking agent during its polymerization, and examples of the crosslinking agent include divinylbenzene, methylene bisacrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate. Examples include methacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, and diallyl phthalate. In both polymers (A1) and (A2), it is appropriate to use the crosslinking agent in an amount of 0 to 5 mol%, preferably 0.01 to 3 mol%. If the amount of the crosslinking agent is too large, the water solubility will decrease, which is not preferable.

In the dispersant of the present invention, these sulfonic acid group-containing aromatic hydrocarbon polymers are used in the form of alkaline earth metal salts.

Examples of alkaline earth metal salts include beryllium, calcium, magnesium, and barium salts.

As the polyether compound or its derivative as component (B), one obtained by adding an alkylene oxide containing ethylene oxide as an essential component to a compound having an aromatic ring and active hydrogen in the molecule is used. here,
Specific examples of compounds having an aromatic ring and active hydrogen in the molecule include the following.

(1) Phenol, cresol, tert-butylphenol, octylphenol.

Monohydric alcohols such as nonylphenol, dinonylphenol, dodecylphenol, xylenol, naphthol, methylnaphthol, butylnaphthol, paracumylphenol (2) benzyl alcohol.

(3) Polyhydric alcohols such as catechol, resorcinol, pyrogallol, bisphenol A, and phenol-formalin condensates.

(4) Monobasic carboxylic acids such as benzoic acid, phenylacetic acid, buenoxyacetic acid, and toluic acid.

(5) Polybasic carboxylic acids such as phthalic acid and trimellitic acid.

(6) salicylic acid, cresotic acid, oxynaphthoic acid,
Hydroxycarboxylic acids such as D, L-mandelic acid and benzylic acid.

(7) Monovalent amines such as aniline, toluidine, naphthylamine, benzylamine, phenetidine, and cresidine.

(8) Toluylene diamine, phenylene diamine, tolidine base (9) Aminocarboxylic acids and aminophenols such as anthranilic acid.

(10) Mercaptans such as thiophenol, thiosalicylic acid, and benzyl mercaptan.

(11) Ethylene oxide is used alone or together with other alkylene oxides as the alkylene oxide added to amides such as acetanilide and benzamide, which have an aromatic ring and active hydrogen in their molecules.

The proportion of ethylene oxide in all alkyl oxides is 7
A suitable range is 0 to 100% (weight %), more preferably 80 to 100%. As the alkylene oxide other than ethylene oxide, propylene oxide, butylene oxide, etc. are used.

In the present invention, in addition to such polyethers, derivatives of this polyether can also be used as component (B). Examples of this derivative include cross-linked products of polyether with terminal hydroxyl groups and products modified with terminal hydroxyl groups.

Crosslinking of polyether terminals can be carried out using radical generators such as benzoyl peroxide, hydrogen peroxide, and peracetic acid; polyhydric carboxylic acids such as maleic acid, fumaric acid, and phthalic acid; and tolylene diisocyanate, toridine diisocyanate, and hexamethylene diisocyanate. Epoxy compounds such as incyanate; diglycidyl bisphenol A, etc. can be used.

When using a radical generator, it can be used in an amount of 0.05 to 10% by weight based on the polyether, and crosslinking can be carried out at a temperature of 40 to 200°C.

In the case of polyhydric carboxylic acid, the terminal hydroxyl group 1 of polyether
Use 0.05 to 0.3 mol, 80 to 25
It can be carried out at a temperature of 0°C.

When using an isocyanate or epoxy compound, it is 0.05 to 0.5 with respect to the terminal hydrogen group of the polyether.
It can be carried out using molar amounts and at a temperature of 50 to 150°C.

Examples of modification of polyether terminals include phosphoric acid esterification and sulfuric acid esterification.

For phosphoric acid esterification, apply a phosphoric acid esterifying agent such as phosphorus pentoxide to the terminal hydroxyl group of polyether at a rate of 0.05 to 0.
．． It can be carried out using 4 mol at a temperature of 50 to 100°C.

Sulfuric acid esterification uses a sulfuric acid esterifying agent such as chlorosulfonic acid, oleum, sulfuric anhydride, or sulfamic acid.
It can be carried out at a temperature of 0 to 150°C.

The polyether compound or its derivative as component (B) is
The weight average molecular weight is preferably 500 to s, ooo, preferably 600 to s, ooo.

As the sulfonated product of component (C) or its salt, the following can be used alone or in combination.

(C1): Lignosulfonic acid or an alkaline earth metal salt thereof (C2) A formaldehyde condensate of an aromatic compound containing a sulfonic acid group or an alkaline earth metal salt thereof (C3) A formaldehyde condensate of an aminotriazine compound containing a sulfonic acid group, or The alkaline earth metal salt (C1) of geninsulfonic acid is obtained from sulfur pulp cooking effluent and used as the free acid or alkaline earth metal salt. The degree of sulfonation and molecular weight vary depending on the type of wood, cooking conditions, etc., but are not particularly limited in the present invention.

Examples of the sulfonic acid group-containing aromatic compound (C2) include benzenesulfonic acid, ethylbenzenesulfonic acid, naphthalenesulfonic acid, butylnaphthalenesulfonic acid, creosote oil (a neutral oil with a boiling point of 200°C or higher in petroleum carbonization tar, or its Examples include sulfonated products of alkylated products), and further genin sulfonic acid. After formaldehyde condensation of these alone or in combination of two or more,
By neutralizing as necessary to obtain an alkaline earth metal salt, a formaldehyde condensate of (C2) a sulfonic acid group-containing aromatic compound or an alkaline earth metal salt thereof can be obtained.

Examples of the aminotriazine compound (C3) include melamine, hexaltyrolmelamine, acetoguanamine, and benzoguanamine.

The condensation reaction product of these and formaldehyde is sulfite,
By sulfonation with sulfuric acid, sulfuric anhydride, bisulfite, etc., or by further neutralizing to form an alkaline earth metal salt, (C゛) a formaldehyde condensate of a sulfonic acid group-containing aminotriazine compound or its alkali Earth metal salts can be obtained. It can also be obtained by sulfonating an aminotriazine compound and then condensing it with formaldehyde. Among the components (C3), melamine resin sulfonic acid or its alkaline earth metal salt is preferred.

The degree of condensation of the condensate of component (C) is suitably from 1.1 to 40, preferably from 1.2 to 20.

As the alkaline earth metal salt of component (C), calcium, magnesium, barium, lithium salts, etc. are used.

In the dispersant of the present invention, the above (A) component, (B) component and (C) component are contained in the above (A) component = 20 to 90% by weight.
, component (B) = 1 to 60% by weight, component (C) = 1 to 60
It is desirable to use the amount within the range of % by weight, whereby both the fluidity and the static stability of the carbonaceous fine powder water slurry can be more effectively improved.

The dispersant of the present invention is contained in an aqueous slurry of carbonaceous fine powder.
It is appropriate to add it in an amount of 0.05 to 3% by weight, preferably 0.1 to 2% by weight.

Examples of carbonaceous fine powder include coals such as anthracite, bituminous coal, subbituminous coal, and lignite; petroleum coke, carbon black by-product from chemical plants, carbon black obtained by carbonizing organic matter, and charcoal that are used as energy sources. be done.

In addition, it is preferable to clean coal containing a large amount of ash by deashing and desulfurizing it by flotation, oil agglomeration, or the like. These carbonaceous substances are substantially 1m+
*It is pulverized so that it does not contain anything above 74μm, but in consideration of combustibility as a fuel, the content of 74μm or less is 50μm or less.
It is preferably at least 6% by weight, more preferably 6% by weight or more.
It is 0 to 100% by weight.

A water slurry of carbonaceous fine powder can be obtained by pulverizing carbonaceous material to form a water slurry using a dry pulverization method or a wet pulverization method, and the dispersant is dispersed in an appropriate process so that it is included in the final water slurry. can do. For example, when carbonaceous fine powder is obtained by dry pulverization, a dispersant may be dissolved or dispersed in water, and the fine powder may be added thereto to prepare a highly concentrated water slurry using an appropriate mixing device. Furthermore, when a wet pulverization method is employed, the dispersant may be dispersed in advance in the water used for wet pulverization, or may be dispersed during or after wet pulverization.

The concentration of carbonaceous fine powder in water slurry depends on the type of fine powder,
Although it depends on the average particle size, particle size distribution, etc., it can be sufficiently increased by dispersing the dispersant of the present invention, for example, up to about 80% by weight.

According to the dispersant of the present invention, an alkaline earth metal salt of an aromatic hydrocarbon polymer containing a sulfonic acid group, a specific polyether, and an aromatic condensate such as a lignin sulfonate are combined. By using a sulfonated compound or an alkaline earth metal salt thereof in combination, the fluidity and static stability of the carbonaceous fine powder water slurry can be mutually improved. Therefore, a water slurry with a higher concentration than before can be obtained and can be stored stably for a long period of time. Further, by using an alkaline earth metal salt, it is possible to suppress an increase in slagging and deauring.

The carbonaceous fine powder water slurry added with the dispersant of the present invention is
It is useful not only as a boiler fuel for electric power and general industry, but also as a combustion improver to reduce coke used in blast furnaces and metallurgical furnaces in the steel manufacturing field.

Example A specified dispersant was dissolved in water, and a specified amount of carbonaceous fine powder was added little by little to make a dry base of 4. After adding the entire amount, a homomixer (Tokushu Kika Kogyo type) was added. 3.0 at
Stir at 0 rpm for 10 minutes to make high concentration water slurry
00g was prepared.

Next, the fluidity and static stability of this slurry were evaluated.

(1) Fluidity Viscosity was measured at 25°C using a Brookfield viscometer (rotor Nα3, 60 revolutions, measured after 1 minute)
. Based on the obtained results, fluidity was evaluated as follows.

○: Good Δ: Insufficient ×: Poor (2) Static stability 50.0 g of the above highly concentrated water slurry was mixed into 5
Place in a 0011IQ plastic cylinder at 25°C.
It was stored stationary. After 30 days, replace this cylinder with 10
The slurry was frozen by cooling to 0.degree. C., and cut horizontally at two heights from the bottom of the cylinder, and the carbonaceous concentration of the lower (lower layer) slurry was measured and compared with the one immediately after preparation. Based on the obtained results, the standing stability was evaluated as currently.

○: Good Δ: Insufficient ×: Poor The particle size distribution of the carbonaceous fine powder used to prepare the water slurry is shown in Table 1, and the property analysis values are shown in Table 2.

Table 3 shows the properties of component (A) of the dispersant of the present invention, and (B)
The properties of the components are shown in Table 4, and the properties of component (C) are shown in Table 4.
5.

Table 6 shows the measurement results of the water slurry using the dispersant of the present invention containing components (A), (B), and (C).

In addition, Table 7 shows as comparative examples those without the addition of a dispersant (experiment Nα33) and those using the (A), (B), or (C) component of the present invention alone (experiment Nα34, 35, 36).
, the measurement results for representative examples of known dispersants (Experiments Nn37 and 38) are shown.

(Hereinafter in the margin) Table-1 ・' Table-2 (Hereinafter in the margin) Procedural amendment December 26, 1988 Patent Application No. 179289 2, Title of the invention Dispersant for water slurry of carbonaceous fine powder 3. Relationship with the case of the person making the amendment Patent applicant 5. Columns 6 of "Claims" and "Detailed Description of the Invention" of the specification to be amended, Contents of the amendment (1) Patent of the specification Amend the claims as shown in the attached sheet.

(2) "Polyether" on page 7, line 10 of the specification has been replaced with "polyether with a molecular weight of 500 to s, ooo"
Correct.

(3) On page 12, lines 11-12, the phrase ``obtained'' is corrected to read ``obtained with a molecular weight of 500 to s, ooo, preferably 600 to 5,000''.

(4) At the bottom of page 16, line 65-3 says “(B) component...
...is... ” will be deleted.

7. Attachment to list of attached documents, Attachment to equipment Claim 1, (A): One or more sulfonic acid group-containing aromas selected from the following polymers (A1) and (A2). Total alkaline earth salt of group hydrocarbon polymer (A1): (a) one or two selected from the group of polymerizable aromatic sulfonic acid monomers and (b) the group of polymerizable hydrocarbon monomers A polymer obtained by polymerizing more than one type of monomer and containing the above-mentioned group (a) monomer as an essential component (A''): one type selected from the group of polymerizable hydrocarbon monomers or A polymer obtained by polymerizing two or more types of monomers, which is obtained by sulfonating a polymer containing at least one polymerizable aromatic monomer as an essential component.

(B): Molecular weight 500-s obtained by adding alkylene oxide containing ethylene oxide as an essential component to a compound having an aromatic ring and active hydrogen in the molecule,
ooo polyether compound or its derivative; (C): at least one sulfonated product selected from the following (C1), (C2) and (C3) or an alkaline earth metal salt thereof (C"): lignin sulfone Acid or alkaline earth metal salt thereof (C2) Formaldehyde condensate of an aromatic compound containing a sulfonic acid group or an alkaline earth metal salt thereof (C3) Formaldehyde condensate of an aminotriazine compound containing a sulfonic acid group or an alkaline earth metal thereof A dispersant for water slurry of carbonaceous fine powder, characterized by containing a salt.

Claims (1)

[Claims] 1. (A): One or more sulfonic acid group-containing aromatic hydrocarbon polymers selected from the following polymers (A^1) and (A^2): Combined alkaline earth metal salt (A^1): one or more monomers selected from (a) a polymerizable aromatic sulfonic acid monomer group and (b) a polymerizable hydrocarbon monomer group A polymer obtained by polymerizing the above-mentioned group (a) monomer as an essential component (A^2): one or more selected from the group of polymerizable hydrocarbon monomers. (B): a polymer obtained by polymerizing a monomer containing at least one polymerizable aromatic monomer as an essential component; A polyether compound or a derivative thereof obtained by adding an alkylene oxide containing ethylene oxide as an essential component to a compound having hydrogen, and (C): the following (C^1), (C^2) and (C^3)
At least one sulfonated compound or an alkaline earth metal salt thereof selected from (C^1): Lignosulfonic acid or an alkaline earth metal salt thereof (C^2) A formaldehyde condensate of an aromatic compound containing a sulfonic acid group or its A dispersant for an aqueous slurry of carbonaceous fine powder, comprising an alkaline earth metal salt (C^3), a formaldehyde condensate of a sulfonic acid group-containing aminotriazine compound, or an alkaline earth metal salt thereof.