JPS63268797A - Blended coal and oil - Google Patents

Abstract

PURPOSE:To obtain blended coal and oil, containing fine coal powder, mineral oil, nonionic surfactant and carboxylate and having both inhibitory ability of ash deposition and stabilizing ability. CONSTITUTION:The aimed blended coal and oil containing (A) fine coal powder, (B) mineral oil, (C) an ethylene oxide addition type nonionic surfactant having preferably 5-18 HLB and (D) preferably an ammonium salt of a carboxylic acid consisting of preferably a fatty acid or resin acid at 1/50-1/0.1 weight ratio of the components (C) to (D) so as to provide 0.05-10wt.% total amount of the components (C) and (D).

Description

[Detailed description of the invention] Cover 1 upper Δ ribun 匪 The present invention relates to mixed coal oil compositions.

PRIOR ART AND PROBLEMS Blended coal oil, also called colloidal fuel or colloidal material, is made by stably dispersing fine coal powder (hereinafter referred to as pulverized coal) in hydrocarbon oil. It is widely desired as a future fuel resource and raw material for city gas.

Mixed coal oil is fluid, so like liquid fuels such as petroleum,
Oil can be transported by tanker or pipeline, and compared to coal, it is easier to store and
Many research results have been reported on manufacturing technology because it has many advantages, such as easy handling, no risk of spontaneous combustion, and high calorific value per unit volume, thus reducing transportation costs. It is being

Particularly in recent years, many techniques have been proposed for dispersing coal powder into petroleum using hydrocarbon surfactants.

In such mixed coal oil manufacturing technology, nonionic surfactants, especially ethylene oxide-added nonionic surfactants, are attracting attention as particularly practical ones. In particular, when coal types that are significantly weathered or have a high clay content are used as pulverized coal, grayish-white deposits (hereinafter referred to as natural deposits) are likely to form in combustion equipment, circulation pipes, etc., and this can affect combustion efficiency and equipment performance. It has been found that this has a negative impact on maintenance, and it is hoped that this will be resolved as soon as possible.

Means for Solving the Problems The present invention was made based on the knowledge that addition of a carboxylic acid salt to a mixed coal pond containing a nonionic surfactant as a dispersant suppresses the deposition of natural minerals.

That is, the present invention relates to a mixed coal oil containing fine coal powder, mineral oil, a nonionic surfactant, and a carboxylic acid salt.

As the fine coal powder and mineral oil used in the present invention, those commonly used for mixed coal oils can be used as appropriate. Fine coal powder is not particularly limited, but includes anthracite coal, bituminous coal, subbituminous coal, brown coal, etc., with a particle size of 3 mm or less, especially zero
．． It is 15 mm or less. In particular, in the present invention,
It is also possible to use highly weathered coal types and clay-rich coal types, such as Belga coal, Belair coal, Breasol coal, etc., which have conventionally been difficult to use due to significant natural deposition.

Mineral oils include crude oil, heavy oil, light oil, kerosene, tar oil,
In addition to anthracene oil, oil shale, oil separated from sand oil, etc. can be used as desired. The amount of fine coal powder in the mixed coal oil is 30 to 70% by weight of the total amount of the mixed coal oil.

Examples of the nonionic surfactant of the present invention include ethylene oxide-added nonionic surfactants, esters of fatty acids with polyhydric alcohols such as sorbitan, glycerin, pentaerythritol, and polyglycerin, and alkanolamides. However, combination use with an ethylene oxide-added nonionic surfactant is particularly preferred.

Examples of ethylene oxide addition type nonionic surfactants include alkylene oxide adducts of higher alcohols that require ethylene oxide, alkylene oxide adducts of alkylphenols,
Alkylene oxide adducts of alkylnaphthols, alkylene oxide adducts of phenols or naphthols having an aromatic nucleus, alkylene oxide adducts of esters of various higher carboxylic acids and polyhydric alcohols, alkylene oxide adducts of various higher amines, Alkylene oxide adducts of polyamines and polyimines, alkylene oxide adducts of various higher amides, alkylene oxide adducts of various higher mercaptans, alkylene oxide adducts of various higher carboxylic acids, 2
Block or random polymers of more than one type of alkylene oxide, esters of various higher carboxylic acids and polyalkylene glycols that require polyethylene glycol,
Examples include esters of various higher carboxylic acids and polyhydric alcohols.

Further, crosslinked products of these, formalin condensates, alkyl alkanolamines, etc. can also be used.

Here, "high grade" generally refers to a compound that has a hydrophobic hydrocarbon residue large enough to exhibit properties as a surfactant, and has about 8 to 22 carbon atoms, especially! It means a compound having 2 to 18 saturated or unsaturated hydrocarbon groups. Examples of these hydrocarbon residues are compounds having alkyl groups such as lauryl, stearyl, oleyl and the like.

Of course, it may have a side chain or a phenyl group. Examples of alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like.

Polyhydric alcohols include glycerin, polyglycerin,
Examples include pentaerythritol, sorbitan, mannitan, and sucrose.

Specific examples of nonionic surfactants preferable for the present invention include ethylene oxide adducts of higher alcohols having 12 to 18 carbon atoms, ethylene oxide adducts of nonyl or octylphenol or formalin synthesis thereof, oxidation of higher fatty acids or dimer acids. ethylene adducts, polyamines,
Ethylene oxide, propylene oxide adducts or crosslinked products of polyimine, ethylene oxide or propylene oxide adducts of castor oil or castor oil fatty acids, or crosslinked products thereof, block polymers of ethylene oxide and propylene oxide, etc.
In particular, those having an HLB of 5 to 18.

Examples of the carboxylic acid used in the carboxylic acid salt include various fatty acids, aromatic, alicyclic, and aralkyl carboxylic acids.

The fatty acid carboxylic acid may have a side chain, and has a carbon number of I~
32, preferably 2 to 22, more preferably 4 to I8, a saturated or unsaturated fatty acid, which may have a substituent such as a hydroxyl group or a halogen, a polycarboxylic acid, or a secondary Carbon may have a carboxyl group.

It may also be a condensed carboxylic acid, a partially esterified or amidated carboxylic acid. Examples of specific aliphatic carboxylic acids include acetic acid, butyric acid, valeric acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linoleic acid, erucic acid, isostearic acid, lactic acid, ricinoleic acid,
Maleic acid, malic acid, fumaric acid, tartaric acid, etc., naturally occurring beef tallow fatty acids, soybean oil fatty acids, linseed oil fatty acids,
There are castor oil fatty acids, etc., and as aromatic carboxylic acids,
Examples include benzoic acid, alkylbenzoic acid, salicylic acid, phthalic acid, trimellidic acid, and naphthoic acid. Examples of alicyclic carboxylic acids include terpenoid resin acids such as cyclohexylic acid, tronellic acid, abietic acid, isoabietic acid, and levopimaric acid.

Examples of aralkylcarboxylic acids include phenylacetic acid and the like. It may have a substituent such as an alkyl group or a hydroxyl group.

In addition, copolymers of polyhydric carboxylic acids such as maleic acids, polyacrylic acids, polymethacrylic acids, acrylic acids, methacrylic acids, carboxylic acids having polymerizable unsaturated groups such as maleic acids, and ethylene, styrene, etc. There may be.

Particularly preferred carboxylic acids are higher fatty acids having about I2 to 22 carbon atoms, terpenoid carboxylic acids, and the like.

As the salts of these carboxylic acids, various metals, ammonia, amines, etc. can be used.

As the metals, various metals such as alkali metals such as potassium and sodium, alkaline earth metals such as magnesium and calcium, as well as aluminum, manganese, and copper can be used. Preferred metals are alkali or alkaline earth metals.

The amines include primary amines, secondary amines, and tertiary amines.
The amine may be any class amine, and examples thereof include alkylamines, alicyclic amines, arylamines, aralkylamines, hydroxylamines, amidoamines, polyamines, heterocyclic amines, and the like.

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 1 to 12.

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

Examples of the alicyclic amine include cyclohexylamine, cyclopentylamine, 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, diethylaniline, N,
N-diethyloleylamine, diphenylamine, N-
Examples include methyldiphenylamine, phenylenediamine, and phenylhydroxylamine. Examples of the aralkylamine include benzylamine and N-methylbenzylamine.

As hydroxylamine, monoethanolamine,
In addition to alkanolamines such as jetanolamine, triethanolamine, monopropanolamine, dibropanolamine, and tripropanolamine, monomethylmonoethanolamine, dimethylethanolamine, monobutylmonopropanolamine, monomethyldibrobanolamine, etc. Examples include alkyl alkanolamines.

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 boria and amines 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 preferably 4 to 18 carbon atoms, which may have a side chain. The aromatic amide may be a partially amidated product of benzoic acid and polyamine containing a substituent such as a halogen, alkyl group, hydroxyl group, carboxyl group, or nitro group. 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 ethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, and polyamines having alkyl groups (which may have side chains or unsaturated bonds) as described above. Polyamines obtained by reacting alkyleneimines such as ethyleneimine with aliphatic or aromatic groups having a hydroxyl group such as aromatic polyamines (such as toluidine) (for example, obtained by reacting an alkylamine with ethyleneimine), etc. 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, pyrrole, pyrrolidine, indole, skatole, carbazole, imidazole, oxazole, thiazole, triazine, pyrazole, piperidine, piperazine,
Various examples include pyrimidine, pyranone, 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 may also be polyamines having at least one long-chain alkylamine having 8 to 18 carbon atoms, especially diamines and triamines.

Preferred alkalis for forming carboxylic acid salts include ammonia, lower aliphatic amines, alkanolamines, alkali metals, etc., with ammonia being particularly preferred.

The mixed coal oil composition of the present invention can be added in advance to the oil, mixed with coal, crushed, or injected proportionately into the mixed liquor or separately injected to form salts in the mixed coal oil. You can also do this.

Water may be present in the mixed coal oil. In this case, it may be added with added water and then proportionally injected together with water into oil or mixed liquor. Conversely, it may be added in advance to a portion of the oil constituting the mixed alcoholic beverage, and then proportionally injected into the mixed alcoholic beverage together with the oil.

The weight ratio of nonionic surfactant and carboxylate is 1/50
~I10.1. Particularly preferred is 1/35 to 1/0.3.

The total amount of the nonionic surfactant and carboxylic acid salt added to the above mixed liquor is 0.005 to 10% by weight, preferably 0.01 to 5% by weight, particularly 0.02 to 1% by weight of the total amount of the mixed liquor.
It is.

The composition of the present invention may also contain nonionic, anionic, or cationic surfactants, inorganic salts, organic salts, or water.

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

Example The following ethylene oxide-added nonionic surfactant and carboxylic acid salt were mixed and added to a mixed coal mixture of Saxon Bale coal (particle size -200 mesh 82%) and heavy oil wet-produced using a ball mill. The deposition performance and stability performance were evaluated.

Ethylene oxide addition type nonionic surfactant (1) Stearyl alcohol EO (l 0 mol) adduct (2) Nonylphenol EO (10 mol) adduct (3) Nonylphenol EO (5 mol) adduct formalin condensation (binary body) substance (4) ethylenediamine PO (100 mol) EO (3
2 mol) adduct (5) ACOM-202 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Carboxylate (a) Soybean fatty acid ammonium salt (b) Stearyl fatty acid Na salt (c) Tall oil fatty acid monoethanolamine salt (d) Salt of tall oil fatty acid and polyamine (N, +) partial coconut oil fatty acid amide (f ) Monomethylamine salt of dimer acid (g) Laurylamine salt of cyclohexylate (h) Ammonium salt of abietate Deposition performance After maintaining additive-free Mixed Carbonura 2009 at 70°C and adding a predetermined amount of additives therein. Stir by hand with a spatula. Then, use an autohomogen mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)
This was done by stirring at high speed for 10 minutes at 4000 rpm and measuring the amount of ash attached to the homo mixer blade.

Stability Performance: 500 g of an additive-free mixed coal portion is maintained at 70°C, and a predetermined amount of additives are added thereto, followed by hand stirring with a spatula. Then, use an autohomo mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to
00 rpm+X Stir at high speed for 5 minutes. Wide mouth 25Qml
Put the obtained mixed coal part 2009 in a poly bottle and store it for 64 hours for one week.
After allowing the bottle to stand at 100° C. and then maintaining it vertically for 10 minutes, the ratio (%) of the mixed coal remaining in the polyvinyl bottle was measured.

Effects of the Invention When the mixed coal oil composition of the present invention is used, excellent effects can be obtained in terms of both the ability to suppress natural deposits and the ability to stabilize.

Claims (1)

[Claims] 1. A mixed coal oil containing fine coal powder, mineral oil, a nonionic surfactant, and a carboxylic acid salt. 2. Total amount of both nonionic surfactant and carboxylate is 0.
．． The blended coal oil according to item 1, containing 05 to 10% by weight. 3. The weight ratio of nonionic surfactant and carboxylate is 1/
50 to 1/0.1, the blended coal oil according to item 1. 4. The mixed coal oil according to item 1, wherein the nonionic surfactant is an ethylene oxide-added nonionic surfactant. 5. The first nonionic surfactant whose HLB is 5 to 18
Mixed coal oil as described in section. 6. The mixed carbon oil according to item 1, wherein the carboxylic acid is a fatty acid or a resin acid. 7. The mixed coal oil according to item 1, wherein the alkali forming the carboxylic acid salt is ammonia.