JPS62151492A - Additive for water slurry coal - Google Patents

Abstract

PURPOSE:To provide an additive for coal/water slurry, containing a nonionic surfactant, a formalin-condensed (alkyl)naphthalenesulfonic acid salt and a lignosulfonic acid salt and capable of increasing coal concentration while keeping low viscosity of the slurry. CONSTITUTION:The objective additive contains (A) 3-60(wt)% nonionic surfactant having an HLB of preferably 12-19.8 (e.g. alkylene oxide adduct of alkylphenol, alkylene oxide adduct of higher alcohol, block copolymer of propylene oxide and ethylene oxide, etc.), (B) 10-90% formalin-condensed (alkyl) naphthalenesulfonic acid salt and (C) 5-80% lignosulfonic acid salt.

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION The present invention relates to an additive for water slurry charcoal for producing fluid water slurry charcoal by dispersing fine coal powder in water.

BACKGROUND OF THE INVENTION In recent years, coal as a fuel has begun to be reconsidered in order to conserve petroleum resources. However, since coal is solid, it is inconvenient to handle, and there are major restrictions, especially in terms of transportation. As a solution to this problem, a proposal has been made to slurry coal powder in water (herein referred to as water slurry coal) and transport it through a pipe.

This water slurry charcoal is mainly used as a fuel after being transported, so in order not to impair energy efficiency, it is necessary to use charcoal with as little water content as possible, high fluidity, and excellent rheological properties and dispersion stability. is desirable. Techniques using various surfactants have been proposed to achieve this purpose.

For example, JP-A-57-194036 proposes a technique of blending a nonionic surfactant and other surfactants as additives for water slurry charcoal. Other surfactants include all types of surfactants, including naphthalene, alkylnaphthalene (hereinafter referred to as (alkyl)naphthalene), and formalin condensation of sulfonic acid (with a degree of condensation l). ~20) An example of yarigenin sulfonate is given. However, no examples have been given that specifically demonstrate the effects of this combination.

JP-A-56-21636 discloses a technique in which a formalin condensate of (alkyl)naphthalenesulfonic acid is used as a dispersant for forming an aqueous slurry. This includes (
There is a description that a formalin condensate of (alkyl) naphthalene sulfonic acid and geninsulfonic acid may be used in combination.

The effects of their combination are not particularly described.

JP-A-57-153092 and JP-A-58-6118
No. 0 discloses a technique of using lignin sulfonic acid as an additive for water slurry charcoal. Furthermore, JP-A-58-45287 suggests the combined use of genin sulfonate and an ethylene oxide adduct of alkylphenol. However, the effects of this combination are not particularly described. JP-A-58-17195 discloses a nonionic surfactant having a formalin condensate of (alkyl)naphthalenesulfonic acid and an okynealkylene group (oxyethylene and oxypropylene group). JP-A-59-91195 discloses a technique for using nonionic surfactants having a specific molecular weight and ethylene oxide content as additives for water slurry carbon. ) It is stated that naphthalenesulfonic acid formalin condensate or sodium polygeninsulfonate may be used in combination. However, there is no specific description of specific combination examples or the effects achieved thereby.

Problems to be Solved by the Invention As mentioned above, water slurry coal is an extremely important means for saving petroleum resources, but at the same time, its consumption is enormous and the resources are extremely cheap, coal and water. Therefore, the surfactant itself used for this basically needs to be inexpensive. Furthermore, ``The major factors that affect the price of water slurry coal are transportation costs and combustion energy per unit weight of water slurry coal. It needs to have excellent viscosity and fluidity.

Lowering the viscosity generally causes a problem of impairing dispersion stability. Therefore, the above-mentioned problems must be taken into consideration when developing additives for water slurry charcoal.

Among the surfactants conventionally proposed as additives for water slurry charcoal, the cheapest one is genin sulfonate. However, when lignin sulfonate is used alone (↓ it is possible to obtain water slurry charcoal with a relatively high concentration, the stability is extremely poor and there is almost no practical use. As a strategy (alkyl)
We tried a technology that uses a formalin condensate of naphthalene sulfonic acid in combination with lignin sulfonic acid, but with this combination, the water slurry charcoal becomes extremely viscous at low temperatures (e.g., 5°C), and is unable to adequately respond to temperature changes. Can not.

As another method to solve the above problem, we tried adding a nonionic surfactant to the lignin sulfonate, but when a nonionic surfactant is used in combination, the temperature generally increases (for example,
The viscosity increases as the temperature increases (0°C), and in this case as well, it is not possible to adequately respond to temperature changes.

Means for Solving the Problems In order to solve the above problems, the present inventors have found that a formalin condensate of (alkyl)naphthalene sulfonate and a nonionic surfactant are blended into a lignin sulfonate and each is used individually. higher concentration (e.g. generally 2~
3% by weight), and that it is possible to obtain water slurry charcoal with improved stability and little change in viscosity with respect to temperature.

That is, the present invention provides a water slurry carbon additive containing a nonionic surfactant, a formalin-fused (alkyl)naphthalene sulfonate, and a lignin sulfonate.

In the present invention, as nonionic surfactants, the following alkylene oxide adducts of hydrophobic groups, particularly ethylene oxide adducts, are important.

Examples of the hydrophobic group of the nonionic surfactant include (alkyl)phenols such as alkylphenols having 4 to 12 carbon atoms, specifically butylphenol, octinophenol, nonylphenol, dodenlephenol, etc.
Polycyclic or polyaromatic phenols, such as orthophenylphenol, paraphenylphenol, styrenated (1
~3 mol) Phenol, bisphenols, naphthols, alkylnaphthols, formalin condensates thereof (degree of formalin condensation 1 to 20, especially 2 to 15), (alkyl)phenol formalin condensates (degree of condensation 1 to 20, preferably 2) ~15); Aliphatic or ring alcohols,
For example, alcohols having 8 to 22 carbon atoms which may have aliphatic saturated or unsaturated side chains, cyclohexanol, alkylcyclohexanol and other alicyclic alcohols, mixed alcohols such as lanolin alcohol, alkyl or alkylphenyl Mercaptans, such as aliphatic mercaptans having 8 to 22 carbon atoms such as ocdylmercaptan and dodecyl mercaptan, and mercaptans having 4 to 22 carbon atoms such as dodenulfenylmercaptan! Alkylaromatic mercaptans having 2 alkyl groups; polyalkylene glycols, such as polypropylene glycol (molecular weight 700
~5000), propylene oxide polymers (molecular mtoooo
~20,000), propylene oxide addition polymers of polyamines, e.g. propylene oxide addition polymers of ethylene diamine), chain-extended esters of the above polyalkylene glycols with polycarboxylic acids (e.g. maleic anhydride); aliphatic amides, e.g. lauryl; Amide, stearylamide, oleylamide, palmitic acid bisamide, etc.; Higher fatty acids, such as lauric acid, palmitic acid, stearic acid, oleic acid, erucic acid, behenic acid, ricinoleic acid, etc.; Polyhydric alcohol fatty acid esters, such as sorbitan fat acid ester, glycerin fatty acid ester, pentaerythritol fatty acid ester, polyglyceride,
Examples include dimer acid and the like.

Particularly preferred hydrophobic groups are alkylphenyl, especially nonylphenol, aliphatic alcohols, especially ocdyl alcohol, lauryl alcohol, stearyl alcohol, lauryl alcohol, lanolin alcohol, etc., polypropylene glycols, and polypropylene glycol obtained by reacting polyols such as glycerin with propylene oxide. etc.

As the hydrophilic group of the nonionic surfactant, an addition polymer chain of ethylene oxide is suitable. The number of moles of ethylene oxide added depends on the number of carbon atoms in the hydrophobic group, but is preferably 8 moles or more, with an HLB of 2 or more months, particularly preferably 13 to 20. The weight ratio of ethylene oxide in the nonionic surfactant is 5% by weight or more, preferably 30% by weight or more of the entire molecule including hydrophobic groups, and all of the hydrophilic groups are addition polymer chains of ethylene oxide. Good too.

The molecular weight of the nonionic surfactant is 500 to +00000,
More preferably, it is 600 to 50,000.

Particularly preferred nonionic surfactants include ethylene oxide adducts of alkylphenols, ethylene oxide adducts of higher aliphatic alcohols, and block copolymers of propylene oxide and ethylene oxide.

The formalin condensed (alkyl) naphthalene sulfonate used in the present invention is naphthalene sulfonic acid, having a carbon number of I to 18.
Naphthalene sulfonic acids having an alkyl group such as isopropylnaphthalene sulfonic acid, butylnaphthalene sulfonic acid, otatylnaphthalene sulfonic acid, etc. Nidialkylnaphthalene sulfonic acids such as dibutylnaphthalene sulfonic acid, noamylnaphthalene sulfonic acid, noisopropylnaphthalene sulfonic acid , di(diisobutylmethyl)naphthalenesulfonic acid, etc.: Salts of formalin condensates of (alkyl)tetralinsulfonic acids, such as tetralinsulfonic acid and decyltetralinsulfonic acid. The degree of formalin condensation is 1 to 30, preferably 2 to 20, especially 8 to
Good results are obtained in 15. Salts include alkali metal salts such as lithium salts, sodium salts and potassium salts, ammonium salts, lower amine salts such as methylamine salts, diethylamine salts, trimethylamine salts, ethylamine salts, diethylamine salts, triethylamine salts, etc.
Alkanolamine salts, such as monoethanolamine salts, jetanolamine salts, triethanolamine salts, monoisopropanolamine salts, etc.; alkylalkanolamine salts, such as methylisopropanolamine salts,
Alkaline earth metal salts such as calcium salts, magnesium salts, etc., other heterocyclic compounds such as pyridine salts,
Examples include morpholine salts, but alkali metal salts, particularly sodium salts, are preferred.

Polmarine condensed (alkyl) naphthalene sulfonate contributes to increasing the concentration of water slurry charcoal, and is effective in preventing the increase in viscosity at high temperatures that occurs when nonionic surfactants are used.

As the lignin sulfonate used in the present invention, alkali metal salts, alkaline earth metal salts, ammonium salts, various lower amine salts, alkanolamine salts, lower alkylalkanolamine salts, polyamine salts, etc. of lignin sulfonic acid can be used. In particular, sodium salts, potassium salts, ammonium salts, calcium salts, etc. are preferred.

The above three types of surfactants are used in combination, for example, two or more types of nonionic surfactants, two or more types of polymarine condensed (alkyl) naphthalene sulfonates, and two or more types of surfactants as ligninsulfonates. Good too.

The blending ratio of the above three surfactants is 8 to 60% by weight of nonionic surfactant, especially 10 to 50% by weight, and 10 to 90% by weight of formalin condensed (alkyl) naphthalene sulfonate, especially 20 to 80% by weight. % and lignin sulfonate 5 to 80% by weight, and especially 10 to 70% by weight. In addition to the above three types of surfactants, if desired, other surfactants may be used, such as dialkyl sulfosuccinates, alkylphenolsulfonates, alkylphenolsulfonates, alkylarylsulfonates, ketone compounds, petroleum sulfonates, Higher alkyl sulfonates, sulfuric ester salts of higher alcohols, sulfuric ester salts of alkylphenols, sulfuric ester salts of ethylene oxide adducts of higher alcohols, sulfuric ester salts of ethylene oxide adducts of alkylphenols, JP-A-60-966
Sulfonated products of cyclopentadiene or its polymer as described in JP-A No. 89, JP-A-54-3380
A styrene sulfonate as described in Publication No. 3 may also be blended. Furthermore, in the present invention, bubbles generated during the production of water slurry charcoal may be suppressed by using metal-curved fatty acids, sodium oleate, potassium palmitate, carunium stearate, aluminum stearate, etc. As the antifoaming agent, a silicone antifoaming agent may be used. Examples of silicone antifoaming agents that can be incorporated include those described in JP-A-58-146434. The water slurry charcoal additive of the present invention may further contain other components, such as CMC, methylcellulose, hydroquine methylcellulose, protective colloid agents such as polyacrylates, fluidity regulators, preservatives, etc., as necessary. .

The amount of the water slurry coalfield additive of the present invention to be used varies depending on the particle size of the coal, but in the case of 200 mesh 80% pass pulverized coal, it is sufficient to use 5% by weight or less based on the coal powder, and the particle size of the coal powder is small. It is preferable to increase the amount added. Usually, OI ~ 1.0 weight 1% is used.

The effluent slurry coalfield additive used in the present invention may be dissolved in water in advance and then added to the pulverized coal, or it may be added later to the mixture of pulverized coal and water.

Alternatively, the additive may be adsorbed on pulverized coal in advance and then mixed with water. Coal powder to be slurried with the additive of the present invention has a particle size of 1-1 m or less, but is not limited thereto. The fine coal powder can be applied to various types of coal and residues such as bituminous coal, sub-bituminous coal, and lignite. Also,
It can be applied to flotation or modified coal whose natural properties have been reduced by oil addition.

The present invention will be explained below with reference to Examples.

Example 1 A water slurry charcoal additive having the formulation shown in Table 1 was dissolved in advance in an amount equivalent to 0.8% by weight based on the coal, and added to a water slurry with a coal concentration of 65% by weight. 20 to be %
Add 0 mesh 83% pass coal powder and mix using an autohomogen mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 200 Or, p, m.
A coal slurry was prepared by mixing for 10 minutes. The viscosity of the prepared slurry was measured at 5°C and 50°C using a B-type viscometer.

Stability was determined by transferring the prepared slurry to a 500R measuring cylinder, allowing it to stand at room temperature, and measuring the viscosity of the slurry at the bottom 1/3 after 15 days. The results are shown in Table 2.

Table-2 A: Initial viscosity x within 1,2, B: Initial viscosity x (1,2~
1.5) C: Initial viscosity X (1,5 to 3), D・40 (1
0 cp or more In Table I, EO is ethylene oxide, PO is propylene oxide, PPG is polypropylene glycol, PE
Each G represents polyethylene glycol.

Therefore, Eo.10 indicates an adduct of 10 moles of ethylene oxide, and PO/EO:10/40 indicates an adduct of 1210 moles of propylene oxide and 40 moles of ethylene oxide. Furthermore, P.P.
In the EO adduct of G, PO/E0·50150 indicates that the weight ratio of the polymerized residue of propylene oxide and the polymerized residue of ethylene oxide is 50:50.

Effects of the Invention The water slurry charcoal additive of the present invention can increase the coal concentration of water slurry charcoal while maintaining low fluidity.

In addition, there is little change in fluidity due to temperature changes, and the stability against temperature changes is high.

Claims (1)

[Claims] 1. Nonionic surfactant, formalin condensation (alkyl)
Additive for water slurry carbon containing naphthalene sulfonate and lignin sulfonate. 2. The additive according to item 1, which contains 3 to 60% by weight of a nonionic surfactant, 10 to 90% by weight of a formalin condensed (alkyl)naphthalene sulfonate, and 5 to 80% by weight of a lignin sulfonate. 3. The additive according to item 1, wherein the nonionic surfactant has an HLB of 12 to 19.8. 4. The additive according to item 1, wherein the nonionic surfactant is selected from alkylene oxide adducts of alkylphenols, alkylene oxide adducts of higher alcohols, and block copolymers of propylene oxide and ethylene oxide. 5. The additive according to item 1, wherein the nonionic surfactant has an ethylene oxide content of 30% by weight or more. 6. The additive according to item 1, which has a formalin condensation degree of 5 to 15.