JPS63268798A - Additive for blended coal and oil - Google Patents

Abstract

PURPOSE:To obtain an additive for blended coal and oil, containing resin acid (derivative) and having both inhibitory ability of ash deposition and stabilizing ability. CONSTITUTION:The aimed additive containing resin acid or a derivative thereof consisting of preferably one or more of abietic acid, neoabietic acid, dihydroabietic acid, tetrahydroabietic acid, pimaric acid, levopimaric acid and palustric acid (e.g. ammonia, amines or metallic salts, alkylene oxide derivatives, ester of the resin acid with polyhydric alcohol, alkanolamide of the resin acid or phenol-modified rosin).

Description

[Detailed description of the invention] Industrial applications The present invention relates to an additive for blended carbon.

Conventional technology Coal mixed fuel, also called colloidal fuel or colloidal material, is a product in which pulverized coal (hereinafter referred to as pulverized coal) is stably dispersed in hydrocarbon oil, and the coal can be used in a fluid state. It is widely desired as a future fuel resource and city gas raw material.

Mixed coal is fluid, so like liquid fuels such as oil,
Oil can be transported by tanker or pipeline, is easier to store and handle than coal, has no risk of spontaneous combustion, and has a high calorific value per unit volume, thus reducing transportation costs. Since it has many advantages, many research results regarding its manufacturing technology have been reported.

Particularly in recent years, many techniques have been proposed for dispersing coal powder in stone ponds using surfactants.

The purpose of the above-mentioned proposed stabilizer for mixed coal oil is mostly to disperse pulverized coal in mineral oil, and no consideration has been given to the settling of clayey components mixed in pulverized coal. do not have.

Problems to be Solved by the Invention As mentioned above, various surfactants have been proposed as dispersion stabilizers for blended coal, and some of them have already reached the stage of practical use. It has been found that when coal types with a significant amount of clay or coal types with a high clay content are used, a large amount of deposits are generated on the walls of combustion equipment, circulation vibrators, etc., and this has a negative impact on combustion efficiency and equipment maintenance. . This problem is particularly acute when using nonionic surfactants.

It is an object of the present invention to provide a mixed carbonaceous material which is less likely to generate the above-mentioned deposits (hereinafter referred to as "deposition") and has excellent stability.

SUMMARY OF THE INVENTION The present invention relates to mixed carbon oil additives containing resin acids or resin acid derivatives.

Resin acid is an acid component in rosins obtained by steam distilling raw resin (gum rosin) or extracting pine resin with a solvent or alkali (wood rosin).
Includes abietic acid, neoabietic acid, dehydroabietic acid, pimaric acid, isopimaric acid, parastric acid, lepobimaric acid, etc.

In the present invention, the above resin acids may be used alone, but
Usually mixtures thereof are used, especially rosin.

The rosin may be gum rosin or wood rosin.

It is good if it contains impurities other than resin acid. Alternatively, it may be pine resin itself. It may also be rosin oil.

Although the resin acid or resin acid mixture mentioned above may be used as it is, it is preferably used as a suitable derivative, especially an alkali salt.

As the alkali salt, in addition to ammonia, amines, metals, etc. can be used. The amines may be primary amines, secondary amines, or tertiary amines, including alkylamines, alicyclic amines, arylamines, aralkylamines, hydroxylamines, amidoamines, polyamines, and heterocyclic amines. There are amines, etc.

The alkyl group of the alkylamine is a saturated or unsaturated alkyl group having 1 to 28 carbon atoms which may have a side chain, such as methyl, ethyl, lauryl, stearyl, oleyl,
lyluyl, erucyl, 2-ethylhexyl, etc.,
It may have a substituent such as a hydroxyl group or a halogen.

The number of carbon atoms is preferably 1 to 18, more preferably! ~12.

The amino group may be bonded to a secondary carbon in addition to the terminal carbon. Specific examples of such alkylamines include ethylamine, diethylamine, triethylamine, 2-ethylhexylamine, oleylamine, stearylamine, methylstearylamine, diethyloleylamine, and the like.

Examples of the lipophilic amine include cyclohexylamine, cyclopendelamine, methylcyclohexylamine, and terpene amine.

The arylamine is an amine having an aromatic group which may have a substituent, and the substituent is an alkyl group (for example, methyl, ethyl, nonyl, dodecyl, etc.)
, halogen, hydroxyl group, nitro group, etc. Specifically, aniline, toluidine, xylidine, naphthylamine, N-monomethylaniline, diethylamine, N, N
Examples include -diethylnaphthylamine, diphenylamine, N-methylbenzylamine, phenylenediamine, and phenylhydroxylamine. Examples of the aralkylamine include benzylamine and N-methylbenzylamine.

As hydroxylamine, monoethanolamine,
In addition to alkanolamines such as jetanolamine, triethanolamine, monopropanolamine, dibrobanolamine, and tripropanolamine, monomethylmonoethanolamine, dimedylethanolamine, monopropanolamine, and monopropanolamine Examples include alkyl alkanolamines such as luanone.

The alkanol group is an alkanolamine having 1 to 4 carbon atoms,
An aromatic alkanolamine derived from styrene oxide or the like, or an alkanolamine derived from an aromatic amine such as aniline may be used. Amidamine is a partial condensate of carboxylic acid and polyamine, and carboxylic acid includes aliphatic carboxylic acid, aromatic carboxylic acid,
It may be a heterocyclic carboxylic acid or the like, and may be a polyhydric carboxylic acid or a condensed carboxylic acid. Examples of polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, hexamethylenediamine, ethyleneimine condensates, aliphatic polyamines such as guanidine, heterocyclic polyamines, and aromatic amines such as melamine.

Preferably it is an alkylene diamine or triamine having 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms. When the amide is an aliphatic amide, the aliphatic group is a saturated or unsaturated hydrocarbon group having 1 to 28 carbon atoms, preferably 2 to 22 carbon atoms, and more preferably 4 to 18 carbon atoms, which may have a side chain. . Aromatic amides include substituents such as halogen,
It may be a partially amidated product of benzoic acid and polyamine having an alkyl group, hydroxyl group, carboxyl group, nitro group, etc. It may also be a partial condensate of polyamine and polycarboxylic acid, in which case the amino group should remain. Examples of polyamines include aliphatic polyamines such as those mentioned above, such as polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and pentaethylenehexanone, and polyamines having an alkyl group (which may have a side chain or unsaturated bond). (for example, obtained by reacting an alkylamine with ethyleneimine), aromatic polyamines (such as toluidine), and polyamines obtained by reacting an aliphatic or aromatic group having a hydroxyl group with an alkyleneimine such as ethyleneimine. Alternatively, it may be a compound obtained by reacting an alkylene imine with an alkylene oxide adduct of a polyalkylene glycol or a compound having an aliphatic or aromatic group having active hydrogen, or conversely, an alkylene imine derivative. It may also be a compound obtained by condensing alkylene oxide.

Examples of nitrogen-containing heterocyclic compounds include morpholine, pyridine, virol, pyrrolidine, indole, skatole, carbazole, imidazole, oxazole, thiazole, trianone, pyrazole, piperidine, piperazine,
Various examples include pyrimidine, pyrazine, and purine. These may have a substituent, or
As mentioned above, it may be modified with alkylene oxide, alkylene imine, or the like. Preferred amines are water-soluble lower amines, alkanolamines, and polyamines, and also polyamines having at least one long-chain alkylamine having 8 to 18 carbon atoms, particularly diamines and triamines.

As the metal salt, in addition to alkali metals such as potassium and sodium, alkaline earth metals such as magnesium and calcium, aluminum, manganese, and various metals can be used. Preferred metals are alkali and alkaline earth metals.

Preferred salts include ammonium salts, alkanolamine salts, lower amine salts, polyamine salts, and alkali metal salts, with ammonium salts being particularly preferred.

Other examples of resin acid derivatives are alkylene oxide adducts of resin acids or esters with polyokine alkylene glycols.

The alkylene oxide adduct of 1-nodine is a random or block adduct of ethylene oxide, propylene oxide, etc., or a random or block adduct of 2 or more of ethylene oxide, preferably
-100 mol, more preferably 2 to 30 mol.

Further, esters of resin acids and other polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, sorbitan, pentaerythritol, diglycerin, sucrose, etc., or alkylene oxide adducts thereof, etc. may also be used.

Various alcohols can be used as esthetics. For example, lower alcohols such as methanol and ethanol, higher alcohols such as lauryl alcohol and oleyl alcohol, alcohols with side chains such as 2-ethylhexanol, and alcohols with ring residues such as cyclohexanol can be used. .

It may also be an alkylene oxide adduct of a resin acid amide, especially an ethylene oxide adduct.

Furthermore, alkanolamide of resin acid obtained by reacting resin acid with jetanolamide etc. can also be used.
Alternatively, it may be an alkali salt of a sulfonated product obtained by sulfonating a resin acid.

Among resin acids and resin acid derivatives, particularly preferred are alkali salts of resin acids. The alkali is preferably used in an amount equal to or more than the equivalent amount to the resin acid, and when the resin acid is used in combination with other acids such as oleic acid, stearic acid, linoleic acid, etc., the alkali is used in an amount equal to or more than the acid equivalent.

In the present invention, a plurality of resin derivatives may be used in combination.

In addition, other surfactants, such as anionic surfactants; alkylbenzene sulfonates, petroleum sulfonates,
Dialkyl sulfosuccinates, naphthalene sulfonates, naphthalene sulfonic acid formalin condensates, higher alcohol sulfate salts, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, etc., nonionic surfactants:
It may be used in combination with polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, fatty acid pentaerythritol ester, fatty acid polyglyceride, polyoxyethylene higher amine, and the like.

The mixed coal oil additive of the present invention may be used alone, but since it has a high softening point, it may be necessary to use a suitable solvent such as alcohol, ether, benzene, ketones, carboxylic acids, turpentine oil, petroleum, etc. It may be used after being dissolved in heavy oil, or it may be used after being dispersed in heavy oil or as an emulsion.

Such blended coal oil additives can be added into the oil, mixed with coal, crushed, or injected proportionally or separately into the blended coal oil to eliminate salts in the blended coal oil. It may be possible to do so.

Water may be present in the blended coal oil. In this case, the resin acid or its derivative may be added to the added water in advance, and then proportionally injected together with water into the oil or mixed coal section.

Conversely, it may be added in advance to a portion of the oil constituting the mixed coal section, and then proportionally injected into the mixed coal section together with the oil.

The mixed coal oil additive of the present invention is 0.005 to 4 g for mixed coal.
10% by weight, preferably 0.01-5% by weight.

The additive of the present invention may coexist with other nonionic, anionic, or cationic surfactants, inorganic salts, organic salts, or water.

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

Example: Saxon Bale coal and heavy oil were wet-produced in a ball mill.The following rosin (salt) was added at 1% to the mixed coal part.
Add and mix with an autohomogen mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) for 4 hours.
After stirring at high speed for 5 minutes at 000 rpm, transfer 200 g of the obtained mixed coal to a 250 cc plastic bottle, let it stand at 64°C for a certain period of time, and after maintaining it vertically for 10 minutes, calculate the proportion (%) of the mixed carbon remaining in the plastic bottle. The stability of the mixed coal part was compared by measuring the .

In addition, after adding the additive of the present invention to the same wet-produced mixed coal oil (200 g), it was stirred by hand with a spatula, and then stirred at high speed at 4000 rpm for 0 minutes with an autohomogen mixer while maintaining the temperature at 70°C, so that the additive did not adhere to the stirring blade. The natural adhesion performance was compared by measuring the amount of ash.

Effects of the Invention When the mixed carbon rib additive of the present invention is used, excellent effects can be obtained in both natural deposition suppressing ability and stabilizing ability.

Claims (1)

[Claims] 1. A mixed carbon oil additive containing a resin acid or a resin acid derivative. 2. The mixed carbon oil additive according to item 1, wherein the resin acid contains at least one of abietic acid, neoabietic acid, dihydroabietic acid, tetrahydroabietic acid, pimaric acid, levopimaric acid, and palustric acid. 3. The mixed coal oil additive according to item 1, wherein the resin acid derivative is an alkali salt of a resin acid. 4. The mixed coal oil additive according to item 2, wherein the alkali is ammonia, amines and/or metal salts. 5. The mixed carbon oil additive according to item 1, wherein the resin acid derivative is an alkylene oxide derivative of a resin acid. 6. The mixed carbon oil additive according to item 1, wherein the resin acid derivative is an ester of a resin acid and a polyhydric alcohol. 7. The mixed carbon oil additive according to item 1, wherein the resin acid derivative is an alkanolamide of a resin acid. 8. The mixed carbon oil additive according to item 1, wherein the resin acid derivative is a phenol-modified rosin.