JPH0134480B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an additive for producing a pulverized coal-oil mixture (hereinafter "pulverized coal-oil mixture" will be referred to as "COM") which is obtained by a wet pulverization method and has excellent stability and fluidity. Conventionally, although pulverized coal has a low price per calorific value, it has drawbacks such as difficulty in transportation, difficulty in controlling combustion, low calorific value, and large storage space. However, there were problems 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,
No. 165490, JP-A-57-53594, and JP-A-54-53106
For this purpose, alkylene oxide adducts of polyalkylene imines with 7 to 200 nitrogen atoms, epihalohydrin reactants of polyols with 3 or more hydroxyl groups, and crosslinked polyether compounds with molecular weights of 1,000 to 20,000 are used. However, although these drugs are effective to some extent, their adsorption with coal particles is weak, so if they are stored for a long period of time, the drug effect decreases and the coal particles begin to settle, so they are not suitable for practical use. This was becoming a big problem. Therefore, the present inventors continued intensive research on additives for preparing a more economical COM that maintains stability and fluidity for a long period of time, and as a result, they have come to provide the present invention. be. That is, the number of nitrogen atoms used in the COM obtained by the wet grinding method [a] is 7 to 200, preferably 9 to 200.
A polyether compound obtained by adding an alkylene oxide to a polyalkylene imine or its derivative having 100 atoms as a starting material, a polyvalent isocyanate, a polyvalent epoxy compound,
Molecular weight 1000 to 600,000, preferably obtained by binding with at least one member selected from the group consisting of polyvalent aldehyde, polyvalent carboxylic acid or polyvalent carboxylic acid derivative, peroxide, and formalin.
7,000 to 300,000 bonded polyether compounds, or [B] [Ro-1] Part or all of the terminal hydroxyl groups of the bonded polyether compounds, a sulfating agent, a phosphorylating agent, an organic carboxylic acid,
Carboxylic acid halide, carboxylic acid anhydride, epoxy group-containing compound, vinyl group-containing compound,
A compound obtained by reacting at least one member selected from the group consisting of a monoisocyanate compound, an alkyl halide, an aldehyde, a halogencarboxylic acid, a hydrogen halide, and a phosphorus halide, or [Ro-2] The above-mentioned bonded polyether compound This is an additive for a pulverized coal-oil mixture, characterized in that the main component is a compound obtained by oxidizing some or all of the terminal hydroxyl groups of In the present invention, the coal used for COM is:
For example, various types of coal such as anthracite, bituminous coal, sub-bituminous coal, and lignite can be used, and any coal can be used regardless of its type, production area, chemical composition, or moisture content. The object of the present invention is COM obtained by a wet pulverization method in which such coal is directly pulverized directly in oil using various types of wet pulverizers. Wet pulverization is even better because it improves the stability of COM and prevents spontaneous combustion and dust during pulverization. Moisture in the coal may be removed during coarse crushing, during wet crushing, or after crushing, and there is no problem even if coal containing low moisture is not removed. Judging from combustibility, the particle size of pulverized coal is usually preferably one with an average particle size of 200 microns or less, and even smaller particles.
A particle size of 100 microns or less is preferable, but as far as the physical properties such as the stability of COM are concerned, there is no problem even if the particle size is larger. 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 viscosity will increase and fluidity will be lost, which is undesirable, but if it contains less than 20% is not preferable because the economic benefits associated with the inclusion of pulverized coal are reduced. Therefore, it can contain 20 to 70% by weight, but 30 to 60% by weight.
% by weight is more preferred. In addition, in the present invention, the oil used for COM is
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 separation residue, creosote oil, anthracene oil,
Oils and waste oils commonly used as fuel, such as 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 waste oil from ships, waste oil from general chemical factories, etc., and also includes mixtures of these. Even if you try to prepare COM using only a single oil or a pre-blended oil, it will not work with a single oil (preferably petroleum crude oil or heavy oil).
After making COM, you can mix it with other oils or co-fire it. 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. It is undesirable because it steals the heat of vaporization during combustion 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, the number of nitrogen atoms is 7 to 200, preferably 9 to 200.
What is polyalkyleneimine having 100 pieces? [Encyclopedia of Chemical Technology, 3rd edition, 3rd edition]
13, pp. 156-157] Polyethyleneimine or polypropyleneimine having 7 to 200 nitrogen atoms (e.g. A-1 to I-1 in Table 1, A- in Table 2)
2 to I-2 starting materials), further alcohols,
Addition polymerization of ethyleneimine and/or propyleneimine to a substance having active hydrogen, such as phenols, amines, and carboxylic acids, results in nitrogen atoms of 7 to 7.
200 pieces (Example: J-1 to L-1 in Table 1,
starting materials J-2 to L-2 in Table 2), those having 7 to 200 nitrogen atoms obtained by ammonolysis or aminolysis of dihalogenoalkane, and the derivatives of the polyalkyleneimine mentioned above. , various derivatives of the following items (a) to (g) that are synthesized because the polyalkylene imine has excellent chemical reactivity like ordinary amines, and the number of nitrogen atoms is It has 7 to 200 pieces, preferably 9 to 100 pieces. (a) to (g) below
The reactivity of each term is also listed. (Refer to "Topical Product/Technology Report 080-11 Ethyleneimine and Polyethyleneimine", Chemical Market Research Institute, November 1980) (a) Reaction products with aldehydes and ketones (e.g. N- in Table 1) 1. Starting material N-2 in Table 2) (b) Reaction products with alkyl halides (e.g. the first
Starting materials M-1 in the table and M-2 in Table 2) (c) Reaction products with isocyanates and thioisocyanates (e.g. starting materials P-1 in Table 1 and P-2 in Table 2) (d) Reaction products with substances having active double bonds (e.g. starting materials Q-1 in Table 1 and Q-2 in Table 2) (e) Reaction products with epoxy compounds and epihalohydrins (e.g. R-1 in Table 1, R- in Table 2)
2 starting materials) (f) Reaction products with cyanamides, guanidines, urea, etc. (e.g. starting material S-1 in Table 1) (g) Reaction products with carboxylic acids, acid anhydrides, acyl halides, etc. (e.g. starting materials O-1 in Table 1 and O-2 in Table 2) The alkylene oxide added thereto refers to ethylene oxide, propylene oxide, butylene oxide, etc., and it is preferable to copolymerize propylene oxide and ethylene oxide. In the case of copolymerization, block copolymerization or random copolymerization may be used, or any of the two may be added first, but block copolymerization is more preferable in order to effectively exhibit the surface active ability. The polyether compound thus obtained contains ethylene oxide as alkylene oxide, and its content is 3 to 80% by weight, more preferably 5 to 50% by weight of the polyether compound. Next, in the present invention, the above-mentioned specific polyether compound is bonded. The polyvalent isocyanate compound used when bonding the polyether compound is, for example, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, 1.5 naphthylene diisocyanate, or the like. Similarly, the polyvalent epoxy compound includes, for example, diglycidyl bisphenol A, diglycidyl ethylene glycol, diglycidyl tetraoxyethylene glycol, and the like. Similarly, the polyvalent aldehyde includes, for example, glyoxal. When bonding using a polyvalent isocyanate compound, polyepoxy compound, or polyvalent aldehyde, the proportion used is arbitrary, but generally it is based on the terminal hydroxyl group equivalent of the polyether compound.
0.05 to 5 equivalents, preferably 0.1 to 3 equivalents are used. The bonding conditions include mixing them with the polyether compound and heating at 40 to 150℃, preferably 50℃ under stirring.
Heating is performed in the range of ~120℃, but if necessary,
Acid or base catalysts commonly used for bonding can be used. Similarly, a polycarboxylic acid or a polycarboxylic acid derivative is a carboxylic acid having two active hydrogen atoms,
For example, carboxylic acids having 3 active hydrogens, such as oxalic acid, malonic acid, phthalic acid, maleic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, dimer acid, and 0-phenylene diacetic acid, such as hemimelittic acid. , trimellitic acid, etc.
Carboxylic acids having 4 active hydrogen atoms, such as butanetetracarboxylic acid, pyromellitic acid, ethylenediaminetetraacetic acid, etc. Carboxylic acids having 5 or more active hydrogen atoms, such as acrylic acid polymers, acrylic acid copolymers, methacrylic acid polymers , methacrylic acid copolymers, maleic anhydride polymers, maleic anhydride copolymers, partially saponified products of polymers and copolymers of acrylic esters and methacrylic esters, and anhydrides and acid halides of the above acids. etc. When bonding using a polycarboxylic acid or a polycarboxylic acid derivative, the proportion used is arbitrary, but
Generally, it is used in an amount of 0.05 to 5 equivalents, preferably 0.1 to 3 equivalents, based on the terminal hydroxyl group equivalent of the polyether compound. When using a polyhydric carboxylic acid, the bonding conditions include bonding the polyether compound and the polycarboxylic acid in the presence or absence of an inert solvent and, if necessary, under reduced pressure.
The purpose can be easily achieved by heating and dehydrating at a temperature in the range of 60°C to 250°C, preferably 80°C to 220°C. In this case, a common esterification catalyst can be used to facilitate the reaction. In addition, when using a polyvalent carboxylic acid derivative such as a polyvalent carboxylic acid halide, an inert gas is passed between the polyether compound and the polyether compound in the presence or absence of an inert solvent to facilitate dehydrohalogenation. or at -10°C using a known agent that can easily capture the hydrogen halide produced.
The purpose can be easily achieved by carrying out the reaction at a temperature of 150°C to 120°C, preferably 0°C to 120°C. Similarly, peroxide (radical generating catalyst) is
These include hydrogen peroxide, benzoyl peroxide (benzoyl peroxide), jeter-cyanobutyl peroxide, cumene peroxide, dicumyl peroxide, and the like. When a peroxide is used for bonding, the proportion used can be arbitrarily used within the range of 0.005% to 10% by weight, preferably 0.1% to 5% by weight, based on the polyether compound. For example, in the Journal of Applied Polymer Science, bonding is achieved by applying a peroxide (radical generating catalyst) to a polyether compound.
Vol. 7 pp. 461-468 (1963), etc., and these known techniques can be applied as they are to the connection referred to in the present invention. Generally, the purpose can be achieved by adding a predetermined amount of peroxide to the polyether compound in the presence of a solvent. 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, and the reaction conditions are according to known methods.
The objective can be achieved by reacting hydrogen halide or phosphorus halide with a polyether compound and replacing some or all of the hydrogen atoms of the terminal hydroxyl groups of the polyether compound with halogen atoms. Furthermore, in the present invention, there may be mentioned a specific bonded polyether compound in which part or all of the terminal hydroxyl groups are oxidized with an oxidizing agent. Such oxidizing agents are known ones, such as chromic anhydride,
These include chromic acid mixture (sulfuric acid and dichromate), activated manganese dioxide, etc. The reaction conditions are in accordance with known methods, for example, the reaction temperature is -10°C to 50°C.
C., preferably from 0.degree. C. to 40.degree. C., and the bound polyether compound is oxidized with an oxidizing agent to form an aldehyde, a ketone, and further oxidation to an acid. Alternatively, the purpose can be achieved by converting these acids into salts. The present invention relates to a specific bonded polyether compound, a compound obtained by reacting a part or all of the terminal hydroxyl groups of a specific bonded polyether compound with a specific compound, or a part or all of the terminal hydroxyl groups of a specific polyether compound. The compound obtained by oxidizing the whole with an oxidizing agent is used as an additive for COM (hereinafter referred to as an 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 may be added before, during, or after the coal is milled. In this case too, water may be added. 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 elevated pressure, normal pressure, or reduced pressure degassing, and the stirrer and stirring conditions are not restricted 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 additive of the present invention, a COM with significantly improved stability and fluidity than before can be obtained, and pulverized coal sedimentation hardly occurs even when stored for long periods at high temperatures as well as at room temperature. However, due to the excellent action of the additive of the present invention,
Because there is almost no agglomeration 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, and can further promote the practical use of COM from an economical standpoint. Estimating the reason why the additive of the present invention exhibits excellent effects, the structure of the additive of the present invention is that by bonding a polyether compound with a very large number of side chains, the number of side chains is further increased, resulting in a steric structure. It is characterized by a large bulk, and this feature increases its adsorption to coal. Also,
Regarding terminal modification, terminal groups were introduced to further improve adsorption to coal. In other words, it is thought that the adsorption to coal is not only due to the usual covering by alkylene oxide chains, but also that the covering is extremely increased and improved, or that the structure added by terminal modification further improves the adsorption. It will be done. In particular, in complex structures such as coal, various functional groups are exposed, so the effect is noticeable and stable depending on the size of the cover or the terminal modified structure as in the present invention. This is thought to have significantly improved the oxidation effect. Example 1 Next, the present invention will be explained in more detail with reference to Examples. All "%" in the examples 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, and place the fuel mixture at the top of the cylinder.
A glass rod with a smooth tip (total weight 20 g) with a diameter of 5 mm is dropped vertically through the center guide hole, and the tip penetrates into the mixed fuel before being placed at the bottom of the cylinder. The time it took to reach this point was measured, and this time was taken as the rod penetration time. The shorter this time, the less sedimentation and consolidation of the pulverized coal, resulting in a mixed fuel with excellent fluidity. After the test, remove the 12 cm stopper from the bottom and check the mixed fuel above the drain (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 sample of the lower layer. The rod penetration test and viscosity measurement described above were both conducted at a temperature of 70°C. Tables 1 and 2 show the additives of the invention used in the examples. Table 3 shows the additives shown in Table 1, Table 4 shows the CMC of the additives shown in Table 2, and comparative products.
The stability test results are shown below. As shown in Tables 3 and 4, when the additive of the present invention is used, the rod penetration time is as short as 1.0 to 5.0 seconds even after being left at 70°C for 30 days, and the viscosity of the upper, middle, and lower layers is It was confirmed that there was almost no difference in coal concentration and that homogeneous and stable COM could be obtained. In addition, in Tables 1 and 2, TDI is referred to as tolylene diisocyanate, XDI is referred to as xylene diisocyanate, and DGBP-A is referred to as diglycidyl bishyphenol A.

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[Table] Example 2 In order to compare in more detail than Example 1, the following test was conducted. Add 0.15% of additives to COM produced in a ball mill (properties shown in Table 5), 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 6 shows the additives shown in Table 1 and comparative products, and Table 7 shows the additives shown in Table 2 and comparative products.
The stability test results of COM are shown. As shown in Tables 6 and 7, when the additive of the present invention is used, most of the COM is discharged even after standing still, and both the coal concentration and coal particle size of the remaining COM at the bottom are almost the same as the COM immediately after production. They have the same properties.
On the other hand, the comparative product had a large amount of COM remaining at the bottom.
It was confirmed that the COM properties immediately after manufacture were different and the stability had collapsed.

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Claims (1)

[Scope of Claims] 1 Used in the pulverized coal-oil mixture obtained by wet pulverization method [A] Number of nitrogen atoms: 7 to 200, preferably 9 to 200
A polyether compound obtained by adding an alkylene oxide to a polyalkylene imine or its derivative having 100 atoms as a starting material, a polyvalent isocyanate, a polyvalent epoxy compound,
Molecular weight obtained by binding with at least one member selected from the group consisting of polyvalent aldehyde, polyvalent carboxylic acid, polyvalent carboxylic acid anhydride, polyvalent carboxylic acid halide, peroxide, and formalin.
1,000 to 600,000, preferably 7,000 to 300,000 bonded polyether compounds, or [B] [B-1] Part or all of the terminal hydroxyl groups of the bonded polyether compound, a sulfating agent, a phosphorylating agent, an organic carboxylic acid,
Carboxylic acid halide, carboxylic acid anhydride, epoxy group-containing compound, vinyl group-containing compound,
A compound obtained by reacting at least one member selected from the group consisting of a monoisocyanate compound, an alkyl halide, an aldehyde, a halogencarboxylic acid, a hydrogen halide, and a phosphorus halide, or [Ro-2] The above-mentioned bonded polyether compound An additive for a pulverized coal-oil mixture, characterized in that the main component is a compound obtained by oxidizing some or all of the terminal hydroxyl groups of with an oxidizing agent. 2. The polyether compound used in the pulverized coal-oil mixture obtained by the wet pulverization method contains ethylene oxide as an alkylene oxide, and the content thereof is 3 based on the polyether compound.
Additive for pulverized coal-oil mixtures according to claim 1 in an amount of ~80% by weight, preferably 5-50% by weight.