JPH0453897A - Additive for mixture of finely ground coal and oil - Google Patents

Abstract

PURPOSE:To obtain the title additive improving a long-term stability of a mixture of a finely ground coal and an oil and preventing ash from adhering to an instrument by incorporating a compd. with a phosphate group in the molecule and a specified polyamine as essential ingredients. CONSTITUTION:A compd. with a phosphate group in the molecule or a salt thereof (e.g. a compd. obtd. from lauryl alcohol and phosphoric anhydride) and a polyamine of formula R1-NH-(R2NH)n-R3 (wherein R1 and R3 are each a 1-30C alkyl or acyl or H; R2 is a 2-6C alkylene; n is 1-20) are incorporated as essential ingredients.

Description

[Detailed description of the invention] [Industrial application field]

The present invention is a pulverized coal-oil mixture (hereinafter referred to as COM) for improving stability and preventing coal ash from adhering to various equipment.
It is related to additives for use.

[Conventional technology]

As a conventional additive for COM, for example, JP-A-53-4
There are anionic compounds shown in No. 7405 and No. 53-82809, and polyether compounds shown in JP-A-54-52105 and 54-52106.

[Problem to be solved by the invention]

However, although these had some effect in preventing the sedimentation of coal, they lacked the ability to prevent the sedimentation of coarse coal particles, such as particles larger than 300μ, and in addition,
In particular, there is a problem that the ash contained in the C0M is liberated and adheres to metal parts such as the stirrer. For this reason, there has been a strong desire to develop additives that further improve the stability of COM and prevent ash adhesion.

[Means to solve the problem]

This invention was made by focusing on such conventional problems. As a result of extensive research into additives that maintain long-term stability and prevent ash adhesion, we have found that (A) a compound with a phosphate ester group in the molecule or its salt, and (B) the following - Shipman (I). ) R, -NH-(R2NH)nI'(s-...(I
) In formula 1, R+ and R3 are alkyl groups having 1 to 30 carbon atoms,
Is an acyl group or a hydrogen atom, and R? is an alkylene group having 2 to 6 carbon atoms, and n is an integer of 1 to 20. ] It has been found that an additive for pulverized coal-oil mixtures containing the polyamine shown in the following as an essential component has very excellent effects. (Requirements constituting the means) Component (A) used in the present invention is obtained by phosphoric acid esterification of the polyether compounds and alcohols shown below. The polyether compound uses various alkylene oxides, such as ethylene oxide, propylene oxide,
butylene oxide, etc. (using one or more kinds, -M
Specifically, the addition reaction may be carried out under pressure using a catalyst such as an alkali or an acid. The alkylene oxide may be used alone or in combination of two or more types, and the arrangement order thereof may be independent and either a block copolymerization type or a random copolymerization type may be used. As starting materials for such polyethers, various substances having active hydrogen are effective, such as alcohols having one active hydrogen such as methyl alcohol, ethyl alcohol, isopropyl alcohol, octyl alcohol, oleyl alcohol, etc. Alcohols with two hydrogens, such as ethylene glycol, BoI
/Alcohols having 3 active hydrogens such as ethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, polybutylene glycol, butanediol, pencundiol, hexanediol,
For example, glycerin, butanetriol, hexanetriol, trimethylolpropane, triethanolamine, alcohols with 4 active hydrogen groups, such as diglycene, pentaerythritol, alcohols with 5 or more active hydrogen groups, such as sorbitol, sorbitan, glucose, shu Close, etc. are useful, and even derivatives thereof such as partially esterified alcohols having two or more active hydrogens can be used as long as one or more active hydrogens remain. In addition, amines are also useful, such as amines with one active hydrogen,
Amines having two active hydrogens, such as dimethylamine, N-methyl-laurylamine, etc., such as methylamine,
Ethylamine, propylamine, butylamine, allylamine, amylamine, octylamine, dodecylamine, laurylamine, tetradecylamine, octadecylamine, tallow alkylamine, coconut alkylamine,
Aniline, p-toluidine, m-toluidine, nitroaniline, benzylamine, chloraniline, p-dodecylbenzylamine, cyclohexylamine, etc., amines with 3 active hydrogens, e.g. ammonia, tallow propylene diamine, etc., 4 active hydrogens amines having 5 or more active hydrogens, such as polyamines such as diethylenetriamine, i-diethylenetetramine, tetraethylenepentamine, etc. Polyalkyleneimines are available. Even various derivatives such as partial amides of amines having two or more active hydrogens can be used as long as one or more active hydrogens remain. Carboxylic acids are also useful, including carboxylic acids with one active hydrogen such as acetic acid, lauric acid, oleic acid, stearic acid, carboxylic acids with two active hydrogens such as oxalic acid, malonic acid, phthalic acid, maleic acid, etc. Carboxylic acids with 3 active hydrogens such as glutaric acid, adipic acid, azelaic acid, sebamic acid, dobucanic acid, timer acid, 〇-phenylene diacetic acid, etc. Carboxylic acids with 4 active hydrogens such as hemimellitic acid, trimellitic acid, etc. Acids such as butanetetracarboxylic acid, pyromellitic acid, ethylenediaminetetraacetic acid, and the like are also useful. As the phenols, alkylphenols having 1 to 18 carbon atoms are useful, and formalin condensates of these are also used. These polyether compounds also include crosslinked polyethers in which one or more OH groups remain in the molecule, other than the above-mentioned polynythyl compounds. That is, a polyether compound having two or more OH groups and a polyhydric (more than two active hydrogen) carboxylic acids as explained above, adipic acid dichloride, azelaic acid dichloride, oxalic acid dichloride, phthalic acid dichloride, etc. Those that are reacted with carboxylic acid halides to form intramolecular or intermolecular crosslinks, or those that have two or more OH
polyethers having groups and polyvalent incyanates such as tolylene diisocyanate, metaxylene diisocyanate, hexamethylene diisocyanate, diglycidyl bisphenol A, diglycidyl ethylene glycol,
Various types of crosslinking, such as polyvalent epoxy compounds such as diglycidyltetraoxyethylene glycol, or polyvalent aldehydes such as glyoxal and thiodiacetaldehyde, which are reacted with l f1 or more to achieve intramolecular or intermolecular crosslinking. It may be a thing. The above polyether compounds in which at least one type of OH group remains in the molecule can be used. Next, as the alcohol, primary or tertiary alcohols having 4 or more carbon atoms can be used, such as n-butyl alcohol, n-octyl alcohol, lauryl alcohol, stearyl alcohol, oleyl alcohol, coconut oil reduced alcohol, tallow reduced alcohol, t -butyl alcohol, 2-ethylhexyl alcohol, etc., and
Aromatic alcohols such as benzyl alcohol can also be used. Next, the above method for phosphoric acid esterification of polyether compounds and alcohols involves reacting with a phosphorylating agent such as phosphoric acid, phosphoric anhydride, acetyl phosphoric acid, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, etc. A phosphoric acid ester group is introduced into. At this time, monoesters, diesters, and triesters can be obtained singly or as a mixture by using the phosphorylating agent, but the proportion of each ester is not particularly limited (as long as it has a phosphoric acid ester group in the molecule. The phosphoric acid ester is used as an acid, but preferably as a salt with a counter ion. Examples of the counter ion include metal salts such as sodium, potassium, calcium, and magnesium, ammonia, ethylamine, butylamine, ethylenediamine, triethylenetetramine, monomer, etc. These include alkylamines such as ethanolamine and impropatulamine, polyamines, and alkanolamines.Next, the polyamines shown in component (B) include ethylenediamine, beef tallow propylene diamine, triethylenetetramine, and tetraethylenepentaamine. Min, pentaethylene t
＼Polyamine such as xamine alone or its derivative. Derivatives are reaction products with alkyl halides, such as dodecylpropylene diamine, dodecyltriethylenetetramine, tallow dipropylenetriamine, and the like. Also effective are amide compounds of polyamines and fatty acids, such as octyl acid, stearic acid, oleic acid, especially coconut oil fatty acid and tallow fatty acid. Phosphoric acid ester compound (A) and polyamine (B) of the present invention
The blending ratio of A/B is 9515 to 5/95, preferably 90/10 to 20/80. Coal used for COM includes, for example, anthracite coal, bituminous coal,
Various types of coal such as sub-bituminous coal and lignite can be used, and any type of coal can be used, regardless of its type or production area (or regardless of its chemical composition or moisture content). The coal may be made into pulverized coal directly in oil using various wet pulverizers, or pulverized coal may be made into pulverized coal using a normal dry pulverizer.However, wet pulverization improves the stability of COM. , and it is even better because it can prevent spontaneous combustion and dust during pulverization. Moisture in coal can be removed during dry pulverization, or it can be crushed during wet pulverization or after pulverization, and coal with low moisture content does not need to be removed. Judging from the combustibility, the average particle size of pulverized coal is usually preferably 200 microns or less, and even smaller particle size of 100 microns or less is preferable. As long as the particle size is larger, there is no problem.The content of this fine powder is 20 to 70% by weight based on the final mixture;
If the pulverized coal is contained in excess of 20%, the viscosity will become extremely high and fluidity will be lost, which is undesirable. If it is less than 20%, the economical advantages associated with the pulverized coal content will be reduced, which is not preferred. Therefore, 20 = -70 weights! %, but 30 to 60% by weight is more preferable. In addition, the oil used for C,OM refers to 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, Anne 1
~Oils and waste oils commonly used as fuel, such as screw oil and various blended oils, such as gas station waste oil (automobile lubricating oil, cleaning oil), ironworks waste oil (machine oil, cutting oil, cleaning oil, and mixed oils thereof) ), waste oil from oil tankers and other 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. C using only oil alone or pre-mixed oil
Even if OM is prepared, COM may be made from a single oil (preferably petroleum crude oil or heavy oil) and then other oils may be mixed or co-fired. Water is caused by moisture contained in coal mixed into C0M,
However, it is preferable because the volume of water increases transportation costs, storage pipes, and other ship management costs. On the other hand, a small amount of water is allowed because it has the property of improving the stability of water COM and has the effect of reducing NOx and bidine in the exhaust gas during combustion. Therefore, the total water content is The content is preferably 15% by weight or less, preferably 6% by weight or less, and may not be contained at all.In order to stabilize COM using the additive of the present invention and exhibit the effect of preventing ash adhesion, dry-pulverized pulverized coal is required. You can either mix it in oil and then add additives, dissolve the additive in oil beforehand and then add pulverized coal, or mix the pulverized coal, oil, and additives all at once. , 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.Water may be added in this case as well. 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 0.04 to 0.0% by weight in the mixed fuel.
．． 8% by weight, the upper limit being purely for economic reasons. According to the present invention, when forming a dispersion system consisting of additives, pulverized coal, oil, and optionally water, any temperature can be adopted, for example, mixing at 50 to 120"C, and the mixing pressure is pressurized,
2 Stirrers and stirring conditions are suitable for normal pressure and reduced pressure degassing.
Not subject to restrictions.

[Effect] The effect of the additive of the present invention is that the parent wood groups of component (A) are first aligned and adsorbed to the active sites of coal, thereby preventing particles from coagulating with each other at the active sites and preventing sedimentation. On the other hand, component (B) strongly adsorbs to free ash (clay minerals) due to the cationic nature of the polyamine. Furthermore, the ash particles, which have been made hydrophobic by the hydrophobic groups of the polyamine, are dispersed in the heavy oil and are prevented from adhering to pipe walls and the like. Since the ash particles hydrophobized in this way become a colloidal dispersion and exist in heavy oil in a corrosive state, they are thought to have the effect of preventing coal from settling. Therefore, when component (B) is used in combination with component (A), it not only prevents ash adhesion but also further improves stability. 【Example】

Next, the present invention will be explained in more detail with reference to Examples.
The examples are merely for illustrative purposes and are not intended to constrain the spirit of the invention. As a small-scale model of the stirring section of the C0M manufacturing apparatus, a homo mixer equipped with a stirring spring for high viscosity manufactured by Tokushu Kika Kogyo Co., Ltd. was used, and the ash adhesion prevention test was conducted as follows. COM heated to 90℃ (Properties are shown in [Table 1])
Additives (shown in Table 2) to 0.25% by weight (relative to C)
OM) and premixed with a spatula,
Stir for 10 minutes at the same temperature, 5000 rpm. Subsequently, after cleaning the COM adhering to the stirrer with a solvent, the amount of ash firmly adhering around the rotating part was measured. It can be said that the smaller the ash content, the better the ability to prevent ash adhesion. In addition, the C0M stability test was conducted using the following COM (
0.25% by weight (based on C) of additives (properties shown in Table 1)
OM) and stir for 4 minutes with a homomixer at 4000 rpm. Put the stirred COM into a 500mJ2 poly bottle,
Leave it in a thermostat at 64°C for 10 days. After allowing it to stand still, turn the polybin upside down and dispense the COM. At this time, the weight of COM remaining at the bottom of the plastic bottle and the coal concentration were measured, and the results are shown in Table 3. [As shown in the comparative example in Table 3, phosphoric acid ester [component (A)] alone causes ash adhesion, and C0M
Stability is also not sufficient. When a phosphoric acid ester and a polyamine [component (B)] were blended as in the product of the present invention, a very stable COM without ash adhesion was obtained.

【Effect of the invention】

By using the additive of the present invention, COM that is stable for a long time and does not have ash adhesion can be obtained, COM can be stored in a tank for a long period of time, and there is no ash adhesion to various equipment such as COM pumps and control valves. , mass production and combustion became possible. (Margin below)

Claims (1)

[Scope of Claims] (A) A compound having a phosphate ester group in the molecule or a salt thereof, and (B) the following general formula (I) R_1-NH-(R_2NH)n-R_3...(I)
[In the formula, R_1 and R_3 are an alkyl group having 1 to 30 carbon atoms, an acyl group, or a hydrogen atom, and R_2 is an alkyl group having 1 to 30 carbon atoms, and R_2 is a hydrogen atom having 2 to 30 carbon atoms.
6 alkylene group, and n is an integer of 1 to 20. An additive for a pulverized coal-oil mixture, characterized by containing a polyamine represented by the following as an essential component.