JPH0431496A - Additive for pulverized coal/oil mixture - Google Patents

Abstract

PURPOSE:To obtain the title additive for improving the stability and preventing the deposition of coal ash on various machinery by mixing a compound having sulfo groups in the molecule with a specified polyamine. CONSTITUTION:An additive containing component (A) comprising a compound having sulfo groups in the molecule or its salt; and a polyamine (B) shown by the formula (wherein R1 and R2 are each 1-30C alkyl, acyl or alkylene; n is 1 to 20). The component A is a compound obtained by reacting an organic substance with a sulfonating agent, such as sulfuric acid, fuming sulfuric acid, sulfuric anhydride, chlorosulfonic acid or sodium hydrogen sulfite, to introduce one or more sulfo groups into the molecule. Examples of the compound include an alkylnaphthalenesulfonic acid, an alkylphenolsulfonic acid, a sulfonated higher fatty acid, and an alkylsulfosuccinic ester.

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.

[Problem to be solved by the invention]

However, although these had the effect of preventing coal sedimentation to some extent, their performance was insufficient to prevent the sedimentation of coarse coal particles, such as particles larger than 300μ, and in addition, especially those contained in C0M. There is a problem that ash is released and adheres to metal parts such as the stirrer. For this reason, CO
It has been desired to develop an additive that further improves the stability of M and prevents 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 or its salt that has a sulfonic acid group in the molecule, and (B)
General formula R, -NH-(Rz -NH-) n -Rs (In the formula, R+ and Rs represent an alkyl group, an acyl group, or a hydrogen atom having 1 to 30 carbon atoms, and R2 represents an alkylene group having 2 to 6 carbon atoms. It has been found that an additive containing as an essential component a polyamine represented by the following formula (n is an integer of 1 to 20) has very excellent effects. (Requirements constituting means) Component (A) of the additive used in the present invention is a compound having a sulfonic acid group in the molecule, or a salt thereof. Specifically used compounds include organic substances such as sulfuric acid,
It is a compound that reacts with a sulfonating agent such as fuming sulfuric acid, sulfuric anhydride, chlorosulfonic acid, and acidic sodium sulfite to introduce one or more sulfone groups into the molecule. Broadly divided, they are: ① Substances with an aromatic ring and a sulfone group bonded to the core. ■A sulfone group is bonded to an aliphatic chain bond. These are detailed below. ■ Substances with an aromatic ring in which a sulfone group is bonded to the core are those in which a sulfone group is introduced into a benzene ring, naphthalene ring, anthracene ring, or phenol ring, such as benzene, toluene, xylene, alkyl (C, or more). ) sulfonic acids such as benzene, naphthalene, alkylnaphthalene, anthracene, phenol, alkylphenol, aniline, nitroaniline, and styrene, or salts thereof; particularly preferred are sulfonic acids such as alkylnaphthalene, alkyl (C or higher) benzene, and alkylphenol. Also preferred are sulfonated products of two or more aromatic rings bonded together through various reactions, such as diphenyl, distyrenated phenol, styrene polymer, styrene copolymer sulfonic acids, or salts thereof. Furthermore, the above sulfonic acids are condensed with an aldehyde such as formalin, or are further reacted using various reactions such as polymerization, such as formalin condensates of naphthalenesulfonic acid, formalin of naphthalenesulfonic acids of naphthalenesulfonic acid and alkylphenol. Examples include a condensate, a formalin condensate of alkylphenol and naphthalene sulfonic acid, and a copolymer of styrene sulfonic acid and vinyl acetate. Petroleum sulfonate, which is produced as a by-product during petroleum refining, is also effective. ■Those in which a sulfonic group is bonded to an aliphatic chain bond include alkyl sulfonic acids, alkanesulfonic acids, α-olefin sulfonic acids, sulfonated higher fatty acids, sulfonic acids of higher fatty acid esters, and alkyl sulfonic acids of fatty acid amides. , alkyl sulfosuccinates, and the like. For example, sulfonated higher fatty acids include α-sulfolaurate, α-sulfo-tallow fatty acid salt, and α-sulfostearate, and higher fatty acid esters of sulfonic acid are esterified with higher fatty acids and oxysulfonic acid. I did it,
Examples include esters of oleic acid and oxyethanesulfonic acid. Further, the alkyl sulfonic acid of the fatty acid amide is methyl laurate and N-phenyl tauride stearate. Examples of alkylsulfonic acid esters include di-2-ethylhexylsulfosuccinate and dinonylphenol sulfosuccinate. Next, in the case of the sulfonate salt of ■■, the counter ions of the salt include alkali metals and alkaline earth metals such as Na, Ca, Mg, ammonia, ethylamine, ethanolamine, impropaturamine, laurylamine, etc. Amines such as polyamines are used. Next, what is the polyamine shown as component (B)? Polyamines such as ethylenediamine, tallow propylene diamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc., or their derivatives. Derivatives are reaction products with alkyl halides, such as dodecylpropylene diamine, dodecyltriethylenetetramine, tallow dipropylenetriamine, and the like. Also, polyamines and fatty acids, such as octyl acid,
Stearic acid, oleic acid, and especially amide compounds with coconut oil fatty acid and beef tallow fatty acid are effective. The blending ratio of sulfonic acid (A) and polyamine (B) of the present invention is A/B=9515 to 5/95. Preferably 90/1
0 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, origin, chemical composition, or moisture content. Such coal is put into oil as it is or after being crushed,
It may be made into pulverized coal directly in oil using various wet pulverizers, or it may be made into pulverized coal using a conventional dry pulverizer. However, a wet pulverization method is better because it improves the stability of COM and prevents 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 (but there is no problem even if it is not removed if the coal has a low moisture content. The particle size of pulverized coal is determined based on combustibility. Normally the average particle size is 2
A particle size of 00 microns or less is preferable, and a smaller particle size of 100 microns or less is preferable, but as far as physical properties such as COM stability are concerned, even larger particle sizes are acceptable. The content of this fine powder is between 20 and 70% of the final mixture.
If the pulverized coal content exceeds 70% by weight, the viscosity will be extremely high (and fluidity will be lost, which is undesirable. If the pulverized coal content exceeds 70% by weight, the economical advantages associated with the pulverized coal content will be reduced). unfavorable because it decreases, 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 for COM refers to petroleum crude oil, various fractions obtained from crude oil, such as kerosene, light oil, A heavy oil, B heavy oil, C
Oils and waste oils commonly used as fuel such as heavy oil, ethylene decomposition residual oil, creosote oil, anthracene 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 mixtures thereof), waste oil from oil tankers and other ships, waste oil from general chemical factories, etc., and also includes mixtures of these oils. Among them, it is preferable to use petroleum crude oil, B heavy oil, and C heavy oil. C using only oil alone or pre-blended oil
Even if OM is prepared, COM may be prepared from a single oil (preferably petroleum crude oil or heavy oil) and then mixed or co-fired with another oil. Water is caused by moisture contained in coal mixed into C0M,
There are cases where manufacturers or users add water, but transportation costs, storage costs, and other general and administrative costs will increase by the volume of water.
Furthermore, it steals the heat of vaporization during combustion and increases heat loss, which is undesirable, and the less the better. On the other hand, since it has the property of improving the stability of water COM and has the effect of reducing NOx and vizine in the exhaust gas during combustion, a small amount of water is allowed to be mixed in. 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. In order to stabilize COM and exhibit the ash adhesion prevention effect using the additive of the present invention, the additive is added after dry-pulverized pulverized coal is mixed into oil. Either add pulverized coal that has been pulverized, or mix the pulverized coal, oil, and additives all at once (water may be added to each separately. Also, in the case of wet pulverization, add pulverized coal before pulverization. The additive may be added at any time during the pulverization or after the pulverization.Water may also be added in this case.The amount of the additive of the present invention added to the mixed fuel system depends on the coal type, coal particle size distribution, and oil. Although it varies slightly depending on the species, generally 0.01 to 5% by weight in the mixed fuel, preferably 0.04 to 0.
．． 8% by weight, the upper limit being solely 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 can be elevated pressure, normal pressure, or reduced pressure. Even during degassing (the stirrer and stirring conditions are not subject to any restrictions.

[Effect] The effect of the additive of the present invention is that the parent wood groups of component (A) are first oriented 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 hydrophobized 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 are present in the extract in heavy oil, it is 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 equipment, a homomixer equipped with a stirring spring for high viscosity manufactured by Tokushu Kika Kogyo 2 was used, and the ash adhesion prevention test was conducted as follows. Add 0.25% by weight (based on COM) of additives (shown in Table 2) to COM (properties shown in Table 1) heated to 70°C, premix with a spatula, and then add the same Stir for 10 minutes at a temperature of 5000 rpm. Subsequently, after washing the COM that had landed on the stirrer with a solvent, the amount of ash firmly attached around the rotating part was measured. It can be said that the smaller the ash content, the better the ability to prevent ash adhesion. Further, the C0M stability test was conducted as follows. Add 0.25% by weight (relative to COM) of additives to COM (properties shown in Table 1) and stir for 4 minutes using a homomixer at 400 Qrpm. The stirred COM is placed in a 500 mε polybottle and left in a thermostatic chamber 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 polybin and the coal concentration were measured.
The results are shown in Table 3. As shown in the comparative example in Table 3, when the sulfonated product [component (A)] is used alone, ash 4-'r deposition occurs and the C0M stability is also insufficient. When a sulfonated product and a polyamine [component (B)] are blended as in the product of the present invention, ash adhesion does not occur and CO becomes very stable.
M 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. [Table 1] Properties of COM

Claims (1)

[Claims] (A) A compound having a sulfonic acid group in the molecule or a salt thereof, and (B) General formula R_1-NH-(R_2NH)_n-R_
3 (in the formula, R_1 and R_2 represent an alkyl group having 1 to 30 carbon atoms, an acyl group, or a hydrogen atom, and R_2 has a carbon number of 2 to 6
An additive for pulverized coal-oil mixtures, characterized in that it contains as an essential component a polyamine represented by the following alkylene group (n is an integer of 1 to 20).