JPH0139477B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a pulverized coal with excellent stability and fluidity.
This invention relates to additives for producing additives for oil mixtures (hereinafter referred to as "COM"). Conventionally, although pulverized coal has a low price per calorific value, it has drawbacks such as difficulty in transportation, difficulty in controlling thermal sintering, low calorific value, and large storage space. There was a problem with fuel. COM does not have the above drawbacks and has a lower price per calorific value than oil alone, so it has high practical value. However, simply mixing pulverized coal and oil does not provide a satisfactory COM because the pulverized coal particles settle and separate due to the difference in specific gravity, coagulate, and lose fluidity. In order to solve these problems,
165490 and JP-A No. 57-53594, the number of nitrogen atoms is 7.
It has been described that alkylene oxide adducts of ~200 polyalkylene imines and epihalohydrin reactants of polyols having three or more hydroxyl groups are used, but although these agents have some effect, they Due to its weak adsorption with coal, when stored for a long time, the drug's effectiveness decreases and coal particles begin to settle, which has been a big problem in practice. Therefore, the present inventors continued intensive research into additives that can maintain long-term stability and fluidity and adjust more economical COM, and as a result, they were able to provide the present invention. be. That is, [](A) Molecular weight 1000 to 100,000, preferably 3000 to 10
(B) Organic carboxylic acids, carboxylic acid halides, vinyl group-containing compounds, monoisocyanate compounds, alkyl halides, aldehydes, halogen carboxylic acids, hydrogen halides, halogenated A compound obtained by reacting at least one member selected from the group consisting of phosphorus, or [] (A) with a molecular weight of 1,000 to 100,000, preferably 3,000.
This is an additive for pulverized coal-oil mixtures characterized by containing as a main component a compound obtained by oxidizing some or all of the terminal hydroxyl groups of ~100,000 polyether compounds with an oxidizing agent. Examples of coal used for COM include anthracite,
Various types of coal can be used, such as bituminous coal, sub-bituminous coal, and lignite, and any coal can be used regardless of its type, origin, chemical composition, or moisture content. Such coal may be directly pulverized in oil as it is or after being coarsely crushed and pulverized directly in oil using various wet pulverizers, or it may be made into pulverized coal using a conventional dry pulverizer. However, the wet grinding method is better for COM
It is even better because it improves stability and prevents spontaneous combustion and dust during crushing. Moisture in the coal may be removed during dry pulverization, or may be removed during or after wet pulverization, and there is no problem even if coal containing only a small amount of moisture is not removed. As for the particle size of pulverized coal, it is usually preferable to have an average particle size of 200 microns or less, judging from thermal sinterability, and a smaller particle size of 100 microns or less is preferable, but as far as physical properties such as stability of COM are concerned, the particle size is even smaller. There is no problem even if the size is large. The content of this fine powder is 20 to 70% by weight based on the final mixture, and if it contains more than 70% of pulverized coal, the clay content will increase and fluidity will be lost, which is undesirable, but if it contains less than 20% is not preferable because it reduces the economic benefits associated with containing pulverized coal. Therefore, it can contain 20 to 70% by weight, but 30 to 60% by weight.
is even more preferable. In addition, the oils used in COM include petroleum crude oil, various fractions obtained from crude oil, such as kerosene, light oil, A heavy oil, B heavy oil, C heavy oil, etc., ethylene cracked residual oil, creosote oil, anthracene oil, and various blends. Oil and waste oil commonly used as fuel, such as gas station waste oil, (automobile lubricating oil, cleaning oil),
This refers to waste oil from ironworks (machine oil, cutting oil, cleaning oil, and mixtures thereof), waste oil from oil tankers and other ships, waste oil from general chemical factories, etc., and also includes mixtures of these oils. You can adjust the COM by using only a single oil or a pre-blended oil, or you can mix or co-fire with other oils after making the COM with a single oil (preferably petroleum crude oil or heavy oil). Water may be mixed into the COM by the moisture contained in the coal, or added by the manufacturer or user, but transportation costs, storage costs, and other general and administrative costs increase by the volume of water. , which is not preferable because it steals the heat of evaporation during hot firing and increases heat loss, so the smaller the amount, the better. On the other hand, water has properties that improve the stability of COM,
Since it has the effect of reducing NOx and bidine in exhaust gas during combustion, a small amount of it is allowed. Therefore, the total water content is preferably 15% by weight or less, preferably 6% by weight or less, and may not be contained at all. Next, a polyether compound with a molecular weight of 1000 to 100,000 has the general formula Z[(RO)nH]m | Z is the residue of the starting material, R is the alkylene oxide residue, n is the number of moles of alkylene oxide added, m
is a number corresponding to the active hydrogen group of the starting material, and is the number of alkylene oxide bonds to the active hydrogen group. ｜ or those formed by intramolecular or intermolecular bonding with a binder or peroxide (radical generating catalyst), and have at least one hydroxyl group in the molecule, It is a polyether compound with a molecular weight of 1,000 to 100,000, preferably 3,000 to 100,000. These polyether compounds are produced by using at least one of various alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, etc., as a starting material, and generally by using a catalyst such as an alkali or an acid under pressure to form the polyether compounds alone. It is obtained by addition polymerization using block copolymerization type or random copolymerization type. The starting materials for such polyether compounds include various substances having active hydrogen. Various substances having active hydrogen include, for example, alcohols having 1 to 4 active hydrogens, and alcohols having 5 active hydrogens.
amines having 1 to 4 active hydrogens, amines having 5 or more active hydrogens, carboxylic acids having 1 to 4 active hydrogens, carboxylic acids having 5 or more active hydrogens, phenols, These include naphthols, phenols, or naphthols alone or formalin condensates with other aromatic compounds, and have different types of active hydrogens such as carboxyl groups, amino groups, and hydroxyl groups in the same molecule. Next, the binders that form intramolecular or intermolecular bonds are polyvalent (two or more active hydrogen) carboxylic acids,
Polyvalent carboxylic acid halide, polyvalent epoxy compound,
Polyvalent aldehydes, polyvalent isocyanates, etc.
Furthermore, the peroxide (radical generating catalyst) that causes intramolecular or intermolecular bonding is a known peroxide that generates radicals. Polyalkyleneimines having 7 to 200 nitrogen atoms or derivatives thereof are not included as starting materials for the polyether compounds according to the invention. Next, some or all of the terminal hydroxyl groups of a specific polyether compound are combined with organic carboxylic acids, carboxylic acid halides, vinyl group-containing compounds, monoisocyanate compounds, alkyl halides, aldehydes, halogen carboxylic acids, hydrogen halides, and halogenated phosphorus. react with at least one species selected from the group consisting of: Such organic carboxylic acids include, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, caprylic acid, coconut fatty acid, stearic acid, oleic acid, glycolic acid, lactic acid, and methoxyacetic acid, benzoic acid, nitrbenzoic acid, salicylic acid, These include monocarboxylic acids having an aromatic ring such as phenyl acetic acid and naphthoic acid, and various monocarboxylic acids such as aliphatic monocarboxylic acids such as naphthenic acid and cyclopentane monocarboxylic acid. These reaction conditions include heating a polyether compound and an organic carboxylic acid, etc. in the presence or absence of an inert solvent at a temperature of 60°C to 250°C, preferably 80°C to 220°C, under reduced pressure as necessary. This goal can be easily achieved by dehydration.
In this case, a common esterification catalyst can be used to facilitate the reaction. The carboxylic acid halide is a halide of the above-mentioned organic carboxylic acid. These reaction conditions consist of a carboxylic acid halide with a polyether compound,
In order to facilitate the dehydrohalogenation reaction in the presence or absence of an inert solvent, an inert gas is introduced or a known agent that can easily capture the generated hydrogen halide is used at -10°C to 150°C.
The purpose can be easily achieved by carrying out the reaction at a temperature of 0°C to 120°C. Vinyl group compounds include, for example, alkenes such as propylene and butadiene, vinyl carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, or salts thereof, methyl acrylate, ethyl acrylate, methyl methacrylate, butyl methacrylate, etc. acrylic esters and methacrylic esters,
Aromatic vinyl compounds such as styrene and α-metal styrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, vinyl halides and vinylidene compounds such as vinyl chloride, vinyl bromide, and vinylidene chloride, vinyl acetate, vinyl propionate, etc. vinyl ester, allyl sulfonic acid,
Sulfonated vinyl compounds such as methacrylsulfonic acid or salts thereof, acrylamide, sulfoethyl methacrylate, and the like. These reaction conditions include mixing a vinyl group-containing compound and a polyether compound, heating the mixture in the range of 0°C to 200°C, generally in the presence or absence of an acid or chlorine catalyst or a radical catalyst, and
By reacting, the purpose can be achieved. Monoisocyanate compounds include, for example, phenyl isocyanate, parachlorophenyl isocyanate, orthochlorophenyl isocyanate,
These include 3.4-dichlorophenyl isocyanate, ethyl isocyanate, n-butyl isocyanate, octadecyl isocyanate, and the like. These reaction conditions are such that a monoisocyanate compound and a polyether compound are mixed, and the reaction temperature is usually 0°C to
By heating in the range of 150℃ and reacting,
Able to achieve purpose. In this case, an acid or basic catalyst can be used if necessary. Alkyl halides include, for example, halogen-substituted hydrocarbons such as methyl chloride, ethyl chloride, butane bromide, and the like. These reaction conditions are: an alkyl halide and a polyether compound are usually heated at 50°C in the presence of a basic catalyst.
The purpose can be achieved by heating in the range of 150°C and causing a reaction. Examples of the aldehyde include formaldehyde, acetaldehyde, enantaldehyde, benzaldehyde, aldehydic acid, and salicylaldehyde. These reaction conditions can be achieved by heating the aldehyde and the polyether compound in the presence of a basic catalyst in the range of 50°C to 150°C to cause the reaction to occur. Halogen carboxylic acids include, for example, chloroacetic acid,
These include fatty acids such as fluoroacetic acid and bromoacetic acid in which the hydrogen atom of the hydrocarbon group is replaced with a halogen atom, or their sodium and potassium salts. These reaction conditions can be achieved by mixing a halogencarboxylic acid and a polyether compound, heating the mixture in the range of 50°C to 150°C in the presence of a basic catalyst, and causing the mixture to react. Hydrogen halide and phosphorus halide are known ones, such as hydrogen bromide, phosphorus pentachloride, phosphorus tribromide, etc., and the reaction conditions are according to known methods. The objective can be achieved by reacting an ether compound and replacing some or all of the hydrogen atoms in the terminal hydroxyl groups of the polyether compound with halogen atoms. Furthermore, in the present invention, part or all of the terminal hydroxyl groups of a specific polyether compound are oxidized with an oxidizing agent. Such oxidizing agents are known ones, such as chromic anhydride, chromic acid mixture,
(sulfuric acid and dichromate), activated manganese dioxide, etc. The reaction conditions are according to known methods,
For example, reaction temperature -10°C to 50°C, preferably 0°C
to 40°C, polyether compounds are oxidized by an oxidizing agent to aldehydes, ketones, and further oxidation to acids. Alternatively, the purpose can be achieved by converting these acids into salts. The present invention is a compound obtained by reacting some or all of the terminal hydroxyl groups of a specific polyether compound with a specific compound, or a compound obtained by oxidizing some or all of the terminal hydroxyl groups of a specific polyether compound with an oxidizing agent. The compound obtained is used as an additive for COM (hereinafter referred to as additive). The additive of the present invention may be used as it is or dissolved in a solvent such as isopropyl alcohol or butyl cellosolve petroleum fraction. Further, the additive of the present invention can of course be used alone or in a mixture of the additives of the present invention, but it may also be used in combination with one type or multiple types of other drugs. To stabilize and fluidize COM using the additives of the present invention, the additives can be added to oil by dry-pulverized pulverized coal, or the additives can be dissolved in oil beforehand and then dry-pulverized coal can be added to the oil. Alternatively, the pulverized coal, oil and additives may be mixed all at once, or water may be added to each of them. In the case of wet pulverization, it may be added before pulverization, during pulverization, or after pulverization. Additives may also be used in this case. The amount of the additive of the present invention added to the mixed fuel system is:
Although it varies slightly depending on the coal type, coal particle size distribution, and oil type, it is generally 0.01 to 5% by weight, preferably 0.04 to 0.8% by weight in the mixed fuel, and the upper limit is based solely on economic reasons. According to the invention, when forming a dispersion consisting of additives, pulverized coal, oil and optionally water, any temperature can be adopted, for example mixing at 50-120 °C,
The mixing pressure may be increased pressure, normal pressure, reduced pressure degassing, etc., and the stirrer and stirring conditions are not specified as long as the action of the additive is not inhibited, but strong stirring at a circumferential speed of 2 m/sec or more is particularly preferred. By using the additives of the present invention, COM is characterized by significantly improved stability and fluidity compared to conventional ones, and pulverized coal sedimentation hardly occurs even when stored for long periods at high temperatures, even at room temperature. However, due to the excellent action of the additive of the present invention,
Since there is almost no aggregation of settled pulverized coal, it can be re-fluidized with only simple stirring. Of course, stirring is not necessary for a short period of time (about 15 days). This has made it possible to safely transport COM in tankers over long periods of time, store it in tanks, and transport it through pipelines and piping. Furthermore, the additive of the present invention can be used in a smaller amount than conventional additives, which can further promote the practical application of COM from an economical standpoint. Although it is not clear why the additive of the present invention exhibits excellent effects, by modifying the terminal hydroxyl group of the polyether compound, adsorption to coal is not only due to the action of the alkylene oxide chain, but also due to the addition of the terminal modification. It is thought that this structure further improves adsorption properties. Especially in complex structures such as coal, various functional groups are exposed.
It is thought that by modifying not only the alkylene oxide chains but also the terminals of the present invention, the adsorptivity of these to coal is increased, resulting in an excellent effect. Example 1 Next, the present invention will be explained in more detail with reference to Examples. In the examples, all "%" are based on weight.
The rod penetration test shown in the 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.
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 a glass rod with a smooth tip with a diameter of 5 mm (full weight) through the center guide hole. 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. In addition, after the test, remove the 12 cm stopper from the bottom, and check the mixed fuel above it (i.e., 12 to 18 cm from the bottom).
The mixed fuel in the cylinder at point 2) was taken out and used as an upper layer sample, and its viscosity and coal concentration 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 concentration were measured as a lower layer sample. The rod penetration test and viscosity measurement described above were both conducted at a temperature of 70°C. Table 1 shows the additives of the invention used in the examples. Table 2 shows the stability test results of COM using the additives shown in Table 1 and comparative products. As shown in Table 2, when the additive of the present invention is used, the rod penetration time is 1.0~1.0~ even after standing at 70℃ for 30 days.
It was confirmed that it was as short as 5.0 seconds, and that there was almost no difference in viscosity or coal concentration between the upper, middle, and lower layers, and that a homogeneous and stable COM could be obtained.

【table】

【table】

[Table] Example 2 In order to make a more detailed comparison with Example 1, the following test was conducted. Add 0.15% of additives to COM produced in a ball mill (properties shown in Table 3), and mix it with a homomixer.
Stirred at 4000 rpm for 4 minutes. Stirred COM 500
The mixture was placed in a 64°C thermostat for 10 days. After that, the polyethylene bottle was turned upside down and the COM was taken out, and the weight of the COM remaining at the bottom of the polyurethane bottle, the coal concentration, and the coal particle size (48# on) were measured. Table 4 shows the stability test results of COM using the additives shown in Table 1 and comparative products. As shown in Table 4, when the additive of the present invention is used, most of the COM is discharged even after standing still, and the coal concentration and coal particle size of the remaining COM at the bottom are almost the same as the COM immediately after production. . On the other hand, the comparative product had a large amount of COM remaining at the bottom, and
It was confirmed that the COM properties were different and the stability had collapsed.

【table】

【table】

Claims (1)

[Claims] 1 [](A) Molecular weight 1000 to 100,000, preferably 3000
Part or all of the terminal hydroxyl groups of ~100,000 polyether compounds, (B) organic carboxylic acids, carboxylic acid halides, vinyl group-containing compounds, monoisocyanate compounds, alkyl halides, aldehydes, halogen carboxylic acids, hydrogen halides, A compound obtained by reacting at least one member selected from the group consisting of phosphorus halides, or [] The above (A) molecular weight 1000 to 100,000, preferably 3000
An additive for a pulverized coal-oil mixture characterized by containing as a main component a compound obtained by oxidizing some or all of the terminal hydroxyl groups of a polyether compound of ~100,000 with an oxidizing agent.