JPS6014077B2 - Additive for pulverized coal-oil mixture - Google Patents

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, although pulverized coal has a low price per calorific value, it has disadvantages such as difficulty in transportation, difficulty in controlling combustion, low calorific value, and large storage space. There was a problem with 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 yield a satisfactory pulverized coal-oil mixture because the pulverized coal particles settle and separate due to the difference in specific gravity, coagulate, and lose fluidity. Therefore, it is important to find and develop additives that improve stability and fluidity, and the inventors have already succeeded in overcoming the above problems and finding and developing effective additives. This made it possible to put into practical use a powdered coal-oil mixture.

(Japanese Unexamined Patent Publication No. 53-78207) The present inventors have developed a powdered coal that maintains stability and fluidity for a longer period of time and is more economical.
As a result of intensive research in order to obtain an oil mixture, we discovered and succeeded in producing an additive for a mixture of powdered coal and oil, which will be described later, and succeeded in producing an extremely excellent mixture of powdered coal and oil.

According to the present invention, a powdered coal-oil mixture with significantly improved stability and fluidity than before can be obtained, and even when stored for a long period of time at room temperature or high temperature, precipitation of powdered coal hardly occurs, even if it is slightly Even if this occurs, due to the excellent action of this drug, there is almost no agglomeration of the settled pulverized coal, so
It can be re-liquidized with just a simple rope prayer. Of course, if it is for a short period of time (about 15 days), there is no need for a companion. This has made it possible to safely transport the pulverized coal-oil mixture in tankers over long periods of time, or to transport it through pipelines and piping. In addition, the amount of this drug used was smaller than that of the conventional method, and from an economical point of view, it was possible to further promote the practical application of powdered coal-oil mixtures. The coal used in the pulverized coal-oil mixture refers to various types of coal, such as anthracite coal, kerosene coal, sublime coal, lignite coal, etc., regardless of type or production area, chemical composition, or moisture content. things are also available.

Such coal is either left as it is, or coarsely crushed and placed in oil, and made into pulverized coal directly in oil using various green crushers;
Alternatively, it may be made into pulverized coal using a normal 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 the 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 the combustibility, the particle size of fine coal is usually preferably 200 or less, and even smaller particle size of 100 or less is preferable, but as far as physical properties such as stability of the fine coal-oil mixture are concerned, the particle size may be even smaller. There is no problem even if the size is large. The content of this pulverized coal is 20 to 7% by weight based on the final mixture, and if the pulverized coal is contained in an amount of 7% or more, the viscosity becomes extremely high and fluidity is lost, which is not preferable. If the amount is less than 2% by weight, it is not preferable because the economic advantages associated with the inclusion of pulverized coal are reduced.

Therefore, it can contain 20 to 7% by weight, but 30 to 6% by weight.
Even more preferred is a weight percent of . In addition, the oils used in the powdered coal-single compound include petroleum crude oil, various oils obtained from crude oil, such as kerosene, light oil, A heavy oil, B heavy oil, C heavy oil, etc., ethylene decomposition residual oil, creosote oil, anthracene oil, etc. Oils and waste oils commonly used as fuel such as oil, various blended oils, such as gas station waste oil (automobile lubricating oil, cleaning oil), ironworks waste oil (machine oil, cutting oil, cleaning oil, and mixtures thereof), oil tankers, etc. This refers to other waste oil from ships, waste oil from general chemical factories, etc., and also includes mixtures of these. 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, it is not necessary to make a pulverized coal-oil mixture using a single oil (preferably petroleum crude oil or heavy oil) and then mix other oils. You can mix it up or mix it up. Water may be mixed into the coal-oil mixture due to moisture contained in the coal, or may be added by the manufacturer or user, but transportation costs, storage costs, and other general and administrative costs will be incurred based on the volume of water. This is undesirable because it increases the heat of evaporation during combustion and increases heat loss, so the smaller the amount, 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 the amount of N○k and vizine 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, when about 0.5% to 3% of water is added later together with the drug, stability is often significantly improved. The additive for pulverized coal overnight mixture according to the present invention is [a] di-, mono-, or di-
With monomixed alkyl sulfosuccinate ester salts {
b- It is characterized by containing a compound in which a polyether compound having a molecular weight of 1,000 to 10 is reacted with a polycarboxylic acid or a polycarboxylic acid halide to effect intramolecular or intermolecular crosslinking.

Specific examples of the alkyl sulfosuccinate ester salt described in [a} above include the following.

Sodium dihexyl sulfosuccinate, mono-sodium hexyl sulfosuccinate, di-mono mixed sodium hexyl sulfosuccinate, di-n-octyl sodium sulfosuccinate, mono-sodium n-octyl sulfosuccinate, mono-di-mixed sodium hexyl sulfosuccinate , Sodium di-2-ethylhexylsulfosuccinate, Sodium mono-2-ethylhexylsulfosuccinate, Sodium mono-2-ethylhexylsulfosuccinate, Sodium di-decylsulfosuccinate, Sodium mono-decylsulfosuccinate, Sodium mono-2-ethylhexylsulfosuccinate Mixed-n-decyl sodium sulfosuccinate, di- or mono- or mono-di mixed sodium alkyl sulfosuccinate obtained from alcohols with a distribution of carbon numbers of 6 to 10. Monovalent metal salts corresponding to these, such as ammonium salts and potassium salts, are also effective, but di- or mono-di mixed 12-ethylhexyl sulfosuccinic acid sodium salt is particularly preferred. Hereinafter, specific examples of the crosslinked polyether compound described in 'b) above will be described.

The polyether compound referred to herein refers to a homopolymer or copolymer consisting of an alkylene oxide, such as ethylene oxide, propylene oxide, or butylene oxide, and at least one of ethylene chlorohydrin, ethylene carbonate, and tetrahydrofuran, and a compound containing various active hydrogen groups. The molecular weight is arbitrarily selected from those obtained by polymerizing the above alkylene oxide and at least one of ethylene chlorohydrin, ethylene carbonate, and tetrahydrofuran to a starting material having at least 1, preferably 2 or more, to a predetermined molecular weight.

Here, when performing addition polymerization using two or more types of alkylene oxides, the addition mode may be random or block. However, if the surfactant is a copolymer type, it is generally a block copolymer type, and preferably, ethylene oxide is added to make the terminal a hydrophilic group. It is effective to crosslink such polyether compounds either singly or in combination of two or more thereof, and of course, it is also possible to crosslink a single compound and then blend two or more thereof. The active hydrogen groups mentioned here include alcoholic hydroxyl groups, amino groups, carboxylic acid groups,
Examples of starting materials containing one or more phenolic OH groups include the following.

Examples of alcohols include alcohols with one active hydrogen such as ethyl alcohol, butyl alcohol, and octyl alcohol; alcohols with two active hydrogens such as ethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, and polybutylene glycol. Alcohols with 3 active hydrogen groups such as butanediol, betanediol, hexanediol, etc. Alcohols with 4 active hydrogen groups such as glycerin, butanetriol, hexanetriol, trimethylolpropane, triethanolamine, etc. Alcohols having 5 or more active hydrogen groups, such as glycerin and bentaerythritol, such as solpitan,
Sorbitol, glucose, sucrose, partially saponified polyvinyl acetate, partially saponified polypynylacetate copolymer, cellulose, starch, etc. are useful, as well as partially esterified alcohols having two or more active hydrogens. Even if it is a conductor, it can be used as long as one or more active hydrogen remains.

In addition, examples of amines include amines having one active hydrogen such as dimethylamine and N-methyllaurylamine, amines having two active hydrogens such as methylamine, ethylamine, propylamine hebutylamine, allylamine, amylamine, etc. Octylamine, dodecylamine, laurylamine, tetradecylamine, pentadecylamine, octadecylamine, tallow alkylamine, coconut alkylamine, aniline, p-toluidine, m
- Toluidine, nitroaniline, benzylamine, chloroaniline, p-dodecylbenzylamine, cyclohexylamine, etc., amines with 3 active hydrogens, such as ammonia, tallow propylene diamine, etc., amines with 4 active hydrogens, such as ethylenediamine, tetra Amines having 5 or more active hydrogens such as methylenediamine, hexamethylenediamine, phenylenediamine, benzidine, cyclohexyldiamine, etc., such as diethylenetriamiso, triethylenetetramine, tetraethylenebentamine, etc., are useful; Even various derivatives such as partial amides of amines having active hydrogen can be used as long as one or more active hydrogen remains.

Examples of carboxylic acids include carboxylic acids having one active hydrogen, such as acetic acid, lauric acid, oleic acid, stearic acid, etc., and carboxylic acids having two active hydrogens, such as oxalic acid, malonic acid, phthalic acid, and fumaric acid. , maleic acid,
Glutaric acid, adipic acid, azelaic acid, sebacic acid,
Dodecanedioic acid, dimer acid, phthalic acid, isophthalic acid,
Carboxylic acids with 3 active hydrogens such as terephthalic acid and 0-phenylenediacetic acid; carboxylic acids with 4 active hydrogens such as hemimellitic acid, trimellitic acid, trimesic acid, etc., such as butanetetracarboxylic acid, pyromellitic acid, ethylenediamine Carboxylic acids having 5 or more active hydrogen atoms such as tetraacetic acid, such as acrylic acid polymers, acrylic acid copolymers, maleic anhydride polymers, maleic anhydride copolymers, methacrylic acid polymers, methacrylic acid copolymers, Partially saponified products of polymers and copolymers of acrylic acid and methacrylic acid esters are useful, and various derivatives such as partially esterified products thereof can also be used.

Examples of phenols include phenol, cresol, alkylphenol, resorcinol, cabucol, and hydroquinone, and other compounds having an aromatic PH group include naphthols.

These compounds having an aromatic OH group or their formalin condensates contain at least one phenolic O
Those having an H group are also useful. Furthermore, lactic acid, glycolic acid, N-substituted alkylglycine, glycine, malic acid, monoethanolamine, jetanolamine,
It does not matter if it contains different kinds of active hydrogens in the same molecule, such as tartaric acid and aminoethyl ethanolamine.

In addition, the polycarboxylic acids and polycarboxylic acid halides used for crosslinking here can be the polycarboxylic acids in the above categories, such as adipic acid dichloride, azelaic acid dibromide, oxalic acid dichloride, phthalic acid dibromide, etc. Also useful are halides.

Polyvalent carboxylic acid or polyvalent carboxylic acid halide is OH
It is well known that groups can be crosslinked, and crosslinking can be easily carried out under normal esterification reaction conditions.

The proportion used as a crosslinking agent is arbitrary, but generally it is 0.5 to 5 equivalents based on the terminal hydroxyl group equivalent of the polyether,
Preferably, 0.1 to 3 equivalents are used. The crosslinking conditions are as follows:
When using a polycarboxylic acid, the polyether compound and the crosslinking agent are mixed in the presence or absence of an inert solvent, if necessary, under reduced pressure at a temperature of 60 to 250 oo, preferably 80 to 250 oo.
The purpose can be easily achieved by heating and dehydrating in the range of 2 pi○. In this case, a conventional esterification catalyst can be used to facilitate the reaction. In addition, when using a polycarboxylic acid halide, the polyether compound and the crosslinking agent are passed through an inert gas in the presence or absence of an inert solvent to facilitate dehydrohalogenation, or The objective can be easily achieved by using a known agent that can easily capture the hydrogen halide to be reacted at a temperature of -10 to 150 pm, preferably 0 to 12,000 pm. The present inventors have already found that the drug described in 'b' above exerts an excellent effect alone, and has filed a patent application. However, when these drugs are used in combination with the drug described in {a', We found that it had even better effects and released it.

Furthermore, the additive of the present invention is better when dissolved in a solvent, particularly a lower alcohol such as methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethyl cellosolve, or a mixture of lower alcohol and water. Although it exhibits excellent effects, it can be used without using a solvent. Furthermore, there is no hindrance to the combined use of other surfactants in appropriate amounts.

As is clear from the comparison in the examples below, mono- or di-alkyl sulfosuccinate ester salts alone,
It is not preferable because the stability of the pulverized coal and oil mixture is impaired, and it is essential to use the ingredients described in y and the ingredients described in {b} in combination, and the combined ratio is (a no'b} = 95/5 to 5/ 9 preferably 90/10 to 60/40 or 10/90 to 40
/60.

In order to stabilize and fluidize a pulverized coal-oil mixture using the additive of the present invention, dry-pulverized pulverized coal can be mixed into oil and then added, or the additive can be dissolved in oil in advance and then dry-pulverized. Just add crushed pulverized coal or mix all three at once.
Water may be added to each of them, or the additive may be added to the wet-milled pulverized coal-oil mixture or after it is added to the oil, and in this case, water may also be added. .

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 is generally 0.01 to 5% by weight, preferably 0.08% by weight in the mixed fuel.
~0. The upper limits of 5% and 0.8% by weight are based solely on economic reasons. According to the present invention,
When forming a dispersion consisting of additives, pulverized coal, oil and optionally water, any temperature may be employed, e.g.
The mixing pressure may be elevated pressure, normal pressure, or reduced pressure degassing, and the rope slinging machine and rope slinging conditions are not restricted as long as the action of the additive is not inhibited, but in particular, the mixing pressure may be 2 m/s.
A strong rope with a circumferential speed of ec or more is preferable.

Next, the present invention will be explained in more detail using examples. Note that all parts and percentages shown in the 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 mm and a height of 20 mm.
Use one that has an outlet with a stopper on each layer of the enemy.

Fill this cylinder with the specified mixed fuel to a height of 18 skins from the bottom, cover the top of the cylinder with a lid with a guide hole in the center, and insert a glass rod with a diameter of 5 with a smooth tip through the center guide hole. (Total dead weight: 20 mm) 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 defined as the twill 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 feet from the bottom, take out the mixed fuel above it (i.e., the mixed fuel in the cylinder at a height of 12 to 18 feet from the bottom), and sample the upper layer. The viscosity and coal concentration were measured.

Next, the stopcock located 6 arcs 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 concentration were measured as a lower sample. The above-mentioned test for penetration and measurement of viscosity were both carried out at 70). Example The prescribed amounts of coal, petroleum, additives and water shown in Table 1 were added to 1
After adding it to the container and making a hand tumulus at 7pi0 for about 2 minutes,
Using a homo mixer, the mixture was heated for 10 minutes at a circumferential speed of 3 and a speed of 7/sec to obtain a mixed fuel.

This product was subjected to a static calendar test for 30 days at 7 pi○, followed by a rod penetration test 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 mixed fuel is 70 qo, the rod penetration time after the 30-day static calendar test 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 can be transported by large tanker or tanked. It can be seen that it can withstand long-term storage. Reference Example A mixed fuel was obtained under the same conditions as in the example except that the dispersant was changed.

Table 2 shows the properties of this product before the test and the results after a static pupil test at 70 pm for 30 days. 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. Table 1 (Example)

Claims (1)

[Claims] 1 (a) A di- or mono- or di-mono mixed alkyl sulfosuccinate salt having an alkyl group having 6 to 10 carbon atoms in the molecule, and (b) a polyether compound with a molecular weight of 1,000 to 100,000, and a polyhydric carboxylic acid or An additive for a pulverized coal-oil mixture, characterized in that it contains a compound that is crosslinked within or between molecules by reacting a polyhydric carboxylic acid halide.