JPS5989387A - Additive for mixture of powdered coal with oil - Google Patents

Abstract

PURPOSE:An additive for mixtures of powdered coal with an oil, containing a specific mono- and/or di-alkyl sulfosuccinic acid ester salt(s) and a specific crosslinked polyether compound, and having improved stability and fluidity. CONSTITUTION:An additive for mixltures of powdered coal with an oil containing (A) a mono- and/or di-alkyl sulfosuccinic acid ester salt(s) having a 6-10C alkyl group, preferred example; and/or di or mono/di-2-ethylhexyl sodium sulfosuccinate, and (B) a compound obtained by crosslinking a polyether compound having 1,000-100,000mol.wt. with one or more selected from a polyfunctional isocyanate, polyfunctional epoxy and polyfunctional aldehyde compound. The above-mentioned additive in an amount of usually 0.01-5wt% is added to the mixtures of the powdered coal with oil. The mixing ratio between the components (A) and (B) is usually (95/5)-(5/95).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an additive for pulverized coal-oil mixtures for producing pulverized coal-oil mixtures with excellent stability and fluidity.

Conventionally, 1iIli per charcoal firing fij4 i1
Despite its low price, it has drawbacks such as difficulty in transportation, difficulty in controlling combustion, low calorific value, and large storage space, making it problematic as a fuel. A mixture of pulverized coal and oil does not have the above-mentioned drawbacks and has high practical value because it has a lower price per calorific value than oil alone. However, simply mixing pulverized coal and oil does not
Due to the difference in specific gravity, the pulverized coal particles settle and separate, condensing, and losing fluidity, making it impossible to obtain a satisfactory pulverized coal-oil mixture.

Therefore, it is important to find an additive that improves stability and fluidity, and the present inventors have already succeeded in overcoming the problems mentioned above and finding an effective additive. This enabled the practical use of charcoal-oil mixtures. (Unexamined Japanese Patent Publication No. 53-
78207) The present inventors have continued their intensive research in order to create a coal-oil mixture that maintains stability and fluidity for a longer period of time and is more economical. W) We have succeeded in discovering an additive for coal-oil mixtures, and we have developed an extremely excellent pulverized coal.
The oil mixture was successfully produced.

According to the present invention, a pulverized coal-oil mixture with significantly improved stability and fluidity compared to conventional ones can be obtained, and even when stored for long periods at high temperatures as well as at room temperature, there is almost no sedimentation of the coal. Even if a few drops occur, due to the excellent action of this agent, sedimentation of pulverized coal will hardly occur, so it can be fluidized with very moderate stirring 1'. Of course, short jlJII? ! l (15
If level B), stir I! There is no need for [.

This has made it possible to safely transport fine coal-oil mixtures over long periods of time in tankers, or to transport them through pipelines and piping. In addition, the amount of this drug used can be reduced compared to conventional ones, and from an economical point of view, the practical application of charcoal-oil mixtures can be further advanced.

The coal used in the pulverized coal-oil mixture is, for example, various coals such as backfill, bituminous coal, sub-bituminous coal, lignite, etc., regardless of the species or place of production, and the coal composition or water content. Regardless, you can also use the ones that hurt.

Such coal may be used as it is, or crushed and placed in oil, and made into fine charcoal directly in the oil using various wet pulverizers, or may be made into pulverized charcoal using an ordinary dry pulverizer. . However, the wet pulverization method is better because it improves the stability of the pulverized coal-oil mixture and prevents spontaneous combustion and dust during pulverization. Moisture in coal may be removed during dry pulverization, or during or after wet pulverization, and if the coal contains a small amount of moisture, there is no problem even if it is not removed.

Judging from fuel properties, the particle size of pulverized coal is usually preferably 200μ or less, and even smaller particle size of 100μ or less is preferred, but there are considerations regarding physical properties such as stability of the pulverized coal-oil mixture, and There is no problem even if it is large. Charcoal content is 20 to 70 parts by weight based on the final mixture.
If pulverized coal is contained in an amount of 70% or more by weight, the viscosity becomes extremely high and fluidity is lost, which is not preferable. If it is less than 20% by weight, it is not preferable because the economic advantages associated with the inclusion of pulverized coal decrease. Therefore, 20
Although it can be contained in an amount of up to 70% by weight, 30 to 60% by weight is more preferable.

In addition, the oil used in the coal-oil mixture (15) refers to petroleum crude oil, various fractions obtained from crude oil, such as kerosene, light oil, heavy oil, B heavy oil, C heavy oil, etc., ethylene decomposition residual oil, creosote oil, etc. Oils and waste oils commonly used as fuel such as anthracene oil and various blended oils, such as Ganlin Sukun 1' waste oil (automobile lubricating oil, cleaning oil), ironworks waste oil (machine oil, cutting oil, cleaning oil, and mixed oils thereof), petroleum This refers to waste oil from tankers and other ships, waste oil from general chemical factories, etc., and also includes mixtures of both.

Among them, it is preferable to use petroleum crude oil, B heavy oil, and C heavy oil. Even if a pulverized coal-oil mixture is made using only a single oil or a pre-blended oil, a single oil (preferably petroleum crude oil,
After making a pulverized coal-oil mixture using heavy oil), other oils may be mixed or co-fired.

Water may be mixed into the pulverized coal-oil mixture by the water contained in the coal, or may be added by the manufacturer or user. etc. becomes high and evaporates during combustion! 1 (This is not preferable because it increases heat loss and increases heat loss, so the less the better.

On the other hand, since water has the property of improving the stability of the pulverized coal-oil mixture and the effect of reducing NOx and hydine in the exhaust gas during combustion, a small amount of water is allowed. Therefore, the total water content is preferably 9% by weight or less, preferably 6% by weight or less, and may not be contained at all. However, 0.5%~3
% of water is post-added together with the drug, stability is often significantly improved.

The additive for coal-oil mixtures according to the present invention refers to fat
(b) A polyether compound having a molecule til of 1,000 to 100,000, together with a di-, mono-, or di-mono-containing alkyl sulfosuccinate salt having an alkyl group having 6 to 10 carbon atoms in the molecule. It is characterized by containing a compound crosslinked using at least one selected from isocyanate, polyvalent epoxy, and polyvalent aldehyde compounds.

Specific examples of the alkyl sulfosuccinate salts described in (al) include the following.

Sodium dihexyl sulfosuccinate, sodium mono-hexyl sulfosuccinate, di-mono mixed thorium hexyl sulfosuccinate, sodium di-n-octyl sulfosuccinate, 1-lium mono-n-octyl sulfosuccinate, Dimixture-n-octylsulbosuccinate sl ~ zolium di-2-ethylhexylsulbosuccinate sodium, mono-2-x tylhexylsulbosuccinate f%H-1-IJium, mono-dimixture-2- ethylhexylsulfonylsulfosuccinate, sthorium di-n-decylsulfosuccinate, mono-n-decylsulfosuccinate, mono- and di-mixed sthorium n-decylsulfosuccinate, carbon number 6- Al with 10 distributions:
1 - Sodium di- or mono- or mono-di mixed alkyl sulbosuccinate. In addition, the corresponding ammonium salts, potassium salts, etc. (711) 1i11
Metal salts of i are also effective, but thorium salts of di- or mono-di-mixed-2-ethylhexylsulfosuccinate are preferred.

Hereinafter, specific examples of the crosslinking compound of the polyether compound described in fbl will be described.

The polyether compounds referred to herein include alkylene oxides such as ethylene oxide, propylene oxide, or butylene oxide, homopolymers or copolymers of at least one of ethylene chlorohydrin, ethylene carbonate, and tetrahydrofuran, and various active hydrogen For the starting materials having one or more groups, preferably two or more groups, the above alkylene oxides and ethylene chlorohydrin, ethylene carbonate, tetra-
It is arbitrarily selected from those obtained by polymerizing at least one type of lahydrofuran and binding a predetermined molecule.

Here, when performing the addition using two or more types of alkylene oxides, the addition mode may be random or block.

However, as a general rule, in the case of copolymer type surfactants,
It is common to form a block copolymer, and preferably 4=J of ethylene oxide is added to make the end a hydrophilic group.

Even if such a polyether compound crosslinks 11 monomers, 2
It is also effective to crosslink a mixture of two or more types, and it is of course possible to crosslink a single product and then blend two or more types.

The active hydrogen groups referred to here include alcoholic hydroxyl groups, amino acid groups, carboxylic acid groups, phenolic O1l groups, and the like. Examples of starting materials containing ff or more are:
There are the following:

Examples of alcohols include alcohols containing one active hydrogen such as ethylene glycol, polyethylene glycol, etc., such as ethyl alcohol, methyl alcohol, and octyl alcohol, and alcohols containing two active hydrogens such as ethylene glycol and polyethylene glycol. alcohols having 3 active hydrogen atoms, such as glycerin, butanetriol,
Al having 411N active hydrogen groups such as hexanetriol, trimethylolpropane, 1-liethanolamine, etc.:
Alcohols with 5 or more active hydrogen groups, such as diglycerin, pentaerythritol, etc., such as sorbitan, sorbitol, glutinose, sucrose, saponified polyvinyl acetate, polyvinyl acetate Partially saponified copolymers, cellulose, starch, etc. are useful, and even derivatives such as partially esterified alcohols having two or more active hydrogens,
It can be used if there is any active hydrogen remaining in the open group.

In addition, as amines, active hydrogen 111. Amines containing W, such as dimedylamine and N-methyllaurylamine; amines containing two active hydrogens, such as methylamine, ethylamine, propylamine, butylamine, allylamine, amylamine, octylamine, 1.
-decylamine, laurylamine, tetradecylamine, pentadecylamine, ophtaterylamine, tallow alkylamine, coconut alkylamine, aniline, p-toluidine, m -l-luidine, nitroaniline, benzylamine, chloraniline, p-dodecyl Amines having three active hydrogens such as benzylamine and cyclohexylamine, such as ammonia, beef tallow propylene diamine, etc.
Amines having 4 active hydrogens, such as ethylenediamine, tetramethylenediamine, hexamethylenediamine,
Amines having active hydrogen in 5-opening groups such as phenylene diamine, hendicine, cyclohexyl diamine, etc., such as diethylene I diamine, I diethylene diamine,
Tetraethylenepentamine etc. are useful, and 2 1
Even various derivatives of amines such as partial amines F having 11i1 or more hydrogen atoms can be used as long as one or more open group hydrogen atoms remain.

Examples of carboxylic acids include carboxylic acids having 11+1a active hydrogens, such as acetic acid, lauric acid, oleic acid, stearic acid, etc., and carboxylic acids having 2 active hydrogens,
For example, oxalic acid, malonic acid, phthalic acid, somaric acid, maleic acid, glutaric acid, acyhinic acid, acelaic acid, sebacic acid, dodecanoic acid, dimer acid, fucuric acid, isophthalic acid, terephthalic acid, 0-phenylenediacetic acid, etc. Carboxylic acids having 3 hydrogen atoms, such as hemimelitic acid, trinolytic acid, trimesic acid, etc., carboxylic acids having 4111i1 active hydrogen atoms, such as butanetetracarboxylic acid, pyronolilic acid, ethylenediaminetetraacetic acid, etc., activated water: 1:
Carboxylic acids having 5 open groups, such as acrylic acid polymers, acrylic acid copolymers, maleic anhydride polymers, maleic anhydride copolymers, methacrylic acid polymers, methacrylic acid copolymers, acrylic acid and methacrylic acid esters Partially saponified products of polymers and copolymers are useful, and various derivatives such as partially esterified products thereof can also be used.

Examples of phenols include phenol, cresol, alkylphenol, resorcinol, catechol, and hydroquinone, and other compounds having an aromatic O1l group include naphthol. These aromatic properties 01
Compounds having -1 group or their polymeric condensates having at least one phenolic OH group are also useful.

Furthermore, lactic acid, glycolic acid, N-substituted alkylglycine, glycine, malic acid 1. They may contain different types of active hydrogens in the same molecule, such as monoethanolamine, jetanolamine, tetrateric acid, aminoethylethanolamine, and the like.

In addition, as a polyvalent isocyanate compound, Hekyly'
Methylene diisocyanate, [lylene diisocyanate 1
-, metaxylene diisocyanate, 1゜5 naphthylene diisocyanate, 4,4゛diphenylmethane diisocyanate, etc. Polyvalent epoxy compounds include diglycidyl bisphenol Δ, diglycidyl ethylene glycol, diglycidyl tetra Oxyethylene glycol, etc.

There is another type of aldehyde called glyoxal.

When a crosslinking agent is applied to these polyether compounds, the proportion of the crosslinking agent used is arbitrary, but generally it is in line with the terminal hydroxyl group equivalent of the polyether (1,05
~5 equivalents are used, preferably 0.1 to 3 equivalents.

The crosslinking conditions include mixing the polyether compound and the crosslinking agent, and stirring the mixture to 40-150'C8, preferably 50-1
The addition f4> is carried out at a temperature of 20° C., and if necessary, an acid or base catalyst commonly used for crosslinking can be used.

The present inventors have already found that the drug described in (1+1) alone exhibits an excellent effect, and a patent application is pending, but when these drugs are used in combination with the drug described in 181, an even more excellent effect is exhibited. Furthermore, the additive of the present invention can be used with solvents, particularly methanol, ethanol, isopropanol, n-propanol, isobutanol, n-
It is more effective when dissolved in a lower alcohol such as butanol or ethyl cellosolve, or a mixture of lower alcohol and water, but it can also be used without using a solvent.

Furthermore, there is no hindrance to using other surfactants such as J Tn (>).

As is clear from the comparison in the examples below, mono- or di-alkyl sulfosuccinate salt alone,
This is not preferable because the stability of the pulverized coal-oil mixture is impaired, and it is essential to use the components described in (al) and the components described in fbl in combination, and the combined ratio is (al/(hl-9515~5).
/95, preferably 90/l O to 60/40 or 1
It is 0/90 to 40/60.

In order to stabilize and fluidize a fine charcoal-oil mixture using the additive of the present invention, the additive can be added after dry-pulverized fine charcoal is mixed into the oil, or the additive can be added to the oil in advance. It is sufficient to add pulverized coal that has been melted and then pulverized, or to mix the mixture all at once, and it is also possible to add water to each component.
Wet) Additives may be added later to the crushed pulverized coal-oil mixture or after addition to the oil, and in this case also water addition may be carried out.

The amount of the additive of the present invention added to the mixed fuel system varies slightly depending on the coal type, coal particle size distribution, and oil type, but generally it is 0.01 to 5%, preferably 0.08% in the mixed fuel.
˜0.8% by weight, and the upper limits of 5% and 0.8% by weight are simply values for economic reasons.

According to the present invention, when forming a dispersion system consisting of additives, pulverized coal, ura and, if necessary, water, any temperature is adopted, for example, mixing is performed at 50 to 120°C, and the mixing pressure is pressurized,
The stirrer and stirring conditions are not restricted as long as the action of the additive is not inhibited.
In particular, strong stirring at a circumferential speed of 1 m15 B (- or less) is preferable.

Next, the present invention will be explained in more detail with reference to Examples. Note that all parts and percentages shown in Examples are based on weight. Moreover, the rod penetration test shown in the following examples was conducted as follows.

The test device was a stainless steel cylinder with an inner diameter of 5.5 cm and a height of 20 cm, with a 12cm cylinder at the bottom and 5 cm from the bottom.
Use one that has an outlet with a stopper at each position.

Fill this cylinder with the specified mixed fuel to a height of 18 cm from the bottom, cover the top of the cylinder with a lid with a guide hole in the center, and pass through the center guide hole.
Glass rod with a smooth tip with a diameter of 51111 (total weight 20g)
was dropped vertically, and the time from when the tip penetrated into the mixed fuel until it reached the bottom of the cylinder was measured, and this time was taken as the rod penetration time. The shorter this time, the less sedimentation and compaction of pulverized coal, resulting in a mixed fuel with excellent fluidity.

After the test, remove the stopcock located 12 cm from the bottom, take out the mixed fuel above it (that is, the mixed fuel in the cylinder at a height of 12 to 18 cm from the bottom), and The viscosity and coal concentration of the sample were measured. Next, the stopcock located 6 cm from the bottom was removed, and the mixed fuel above that point was sampled and its viscosity and coal concentration were measured as a middle layer sample. Finally, the bottom stopper was removed, the remaining mixed fuel was collected, and its viscosity and coal II degree were measured as a lower layer sample. Both the rod penetration test and the viscosity measurement described above were conducted at 70°C.

Example The prescribed amounts of coal, petroleum, additives and water shown in Table 1 were added to 1
! After adding to the container and stirring by hand at 70℃ for about 2 minutes,
The mixed fuel was stirred for 10 minutes at a circumferential speed of 3 m/sec and 70° C. using a bomb mixer, and the mixed fuel was dissolved.

After this product was subjected to a static test at 70° C. for 30 days, a rod penetration test was performed and the viscosity and coal concentration of the upper, middle, and lower layers were measured. The results obtained are shown in Table 1.

From Table 1, this fuel mixture has a rod penetration time after a static test of 30 days at 70°C, which is about the same as that immediately after production, and there is little change in viscosity or coal concentration before and after the test, so it is possible to transport it by large tanker or It can be seen that it can withstand long-term storage in a tank.

Reference Example: A mixed fuel was obtained under the same conditions as in the Example except that the dispersant was changed. Properties of this product before testing and 70℃
Table 2 shows the results after a 30-day standing test. Table 2 shows that these mixed fuels cannot withstand transportation in large tankers or long-term storage in tanks because the coal separates and becomes compacted.

(Margin below)

Claims (1)

Scope of Claims: (a1 Di- or mono- or di-mono mixed alkyl sulfosuccinate salt having an alkyl group having 6 to 10 carbon atoms in the molecule and 0 portions -Y-sulfosuccinate, ooo to 100,000 polyesters) An additive for a pulverized coal-oil mixture, comprising a compound obtained by crosslinking an ether compound with at least one selected from polyvalent isocyanates, polyvalent epoxies, and polyvalent aldehyde compounds.