JPH02160899A - Additive used in pulverized coal/oil mixture - Google Patents

Abstract

PURPOSE:To provide the title additive capable of maintaining stability over a long period of time and preventing the adhesion of coal ash to various machinery by using as constituents a specified polyamine and a compound comprising an alkylene oxide adduct of an amine/phenol/formaldehyde condensate. CONSTITUTION:An amine (e.g. methylamine), a phenol (e.g. phenol), and formaldehyde are made to undergo condensation reaction. The condensate is subjected to addition reaction with an alkylene oxide (e.g. ethylene oxide). The title additive is produced by using the compound thus obtained [e. g. of formula I (wherein EO is -CH2-CH2-O-)] and a polyamine of formula II (wherein R1 and R3 are each 1-30C alkyl, acyl or H; R2 is 2-6C alkylene; n is 1 to 20) (e.g. tallow propylenediamine) as the essential constituents, and if necessary, incorporating a solvent, etc., therein.

Description

[Detailed Description of the Invention] Main 1↓ Huangyuri Separation 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.

In the past, Xiaqi Street COM had problems due to sedimentation of coal particles, but this problem was solved with the invention of an excellent stabilizer, and it has already been produced in large quantities and used for combustion as an alternative fuel to petroleum for electric power. ing.

However, with such conventional additives, C
The ash contained in 0M adheres to areas where strong mixing occurs, such as the stirrer, C0M pump, control valves, and elbows of piping, and to areas where the flow rate changes rapidly, and the line must be frequently stopped to scrape off or clean. The need has arisen, and new problems have arisen.

Polyether compounds shown in JP-A-57-165490 and formalin condensates of polyoxyalkylene alkylphenyl ethers shown in JP-A-60-3119 suffer from these problems, and therefore the stability of COM has to be further improved. , there has been a strong desire to develop additives that prevent ash adhesion.

This invention for ``divination'' was made by focusing on these conventional problems.As a result of extensive research into additives that maintain long-term stability and prevent ash adhesion, ( A) A compound obtained by adding an alkylene oxide to a reaction condensate of amines, phenols, and formaldehyde, and (B) - Maximum % formula % (R1, R3: alkyl group or acyl group or hydrogen atom having 1 to 30 carbon atoms, R2 : Alkylene group having 2 to 6 carbon atoms, n=1 to 20) It has been found that an additive containing a polyamine as an essential component is very effective.

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.

- - Component (A) of the additive used in the present invention is a condensed compound containing amines, phenols, and formaldehyde as essential components, with alkylene oxide added,
The raw materials shown below are used.

Examples of amines include alkylamines such as methylamine, butylamine, laurylamine, stearylamine, and oleylamine, aromatic amines such as aniline, benzylamine, toluidine, and phenylenediamine-ophthylamine, and alicyclic amines such as cyclohexylamine. and ethylenediamine,',l-diethylenetetramine. All amines that can be incorporated by condensation reaction with formalin are useful, such as polyamines such as pentaethylenehexamine, and ammonia, viperane, hexamethylenetetramine, hexamethylenetetramine, heptanotanolamine, etc.

Further, secondary amines can also be used in combination with the above amines.

As the phenol, compounds having a phenolic water group such as phenol, alkylphenol, cresol, hydroquinone, naphthol 1 bisphenols, and mixtures thereof with aromatic compounds can also be used.

As the formaldehyde, formalin or rose formaldehyde is generally used. In addition, other aldehydes such as acetaldehyde, butyraldehyde, and henzaldehyde may be used in combination with formaldehyde.

As the alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. are used, but ethylene oxide is most preferred. Copolymers of ethylene oxide and other alkylene oxides may also be used.

Next, the method for producing the additive of the present invention generally involves condensing amines, phenols, and formaldehyde without a catalyst or in the presence of an acid or basic catalyst, and after the condensation, a brine operation is performed.1. Add alkylene oxide. Generally, the molar ratio of amines and phenols is 1/10 to 10/1
1, preferably 115 to 3/1. The molar ratio of (amines + phenols) and formaldehyde is 115~
The ratio is 5/1, preferably 1/3 to 3/1.

The content of alkylene oxide is 20 to 99% by weight, and particularly preferably 30 to 90% by weight of ethylene oxide.

Next, the polyamine shown as component (B) is a polyamine alone or a derivative thereof, such as ethylene diamine, tallow propylene diamine, triethylene tetramine, tetraethylene pentamine, and pentaethylene hexamine. Derivatives are reaction products with alkyl halides, such as dodecylpropylene diamine, dodecyltriethylenetetramine, tallow dipropylenetriamine, and the like.

Also effective are amides of polyamines and fatty acids, such as octyl acid, stearic acid, and oleic acid, especially coconut oil fatty acids and beef tallow fatty acids.

The blending ratio of polyether (A) and polyamine (B) of the present invention is A/B=9515 to 5/95, preferably 90/
lO~50150.

As the coal used for COM, various coals such as anthracite bituminous coal, sub-bituminous coal, lignite coal, etc. can be used, and any coal can be used regardless of the type or production area, or regardless of the chemical composition or moisture content. Such coal may be directly pulverized coal as it is or after being coarsely crushed and placed in oil to be pulverized coal directly in oil using various wet pulverizers, or pulverized coal may be pulverized 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 may be removed during dry pulverization, or may be crushed during wet pulverization or after pulverization, and coal with low moisture content may be removed (but there is no problem. The particle size of pulverized coal is determined based on combustibility. Normally, it is preferable to have an average particle size of 200 microns or less, and even smaller particles of 100 microns or less are preferable, but in terms of physical properties such as the stability of COM, there is no problem even with larger particle sizes. The content is 20 to 70% by weight based on the final mixture, and if it contains 70% or more of pulverized coal, the viscosity will be extremely high and fluidity will be lost, which is undesirable, and if it is less than 20%, pulverized coal will This is not preferable because the economic benefits associated with its inclusion decrease.Therefore, it can be contained in an amount of 20 to 70% by weight, but 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, 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-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,
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 using the additive of the present invention and exhibit the effect of preventing ash adhesion, the additive can be added after dry-pulverized pulverized coal is mixed into oil, or the additive can be melted in oil in advance and then dry-pulverized. Either pulverized pulverized coal may be added, or pulverized coal, oil and additives may be mixed all at once, and 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. In this case as well, water may 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 0.04 to 0.0% by weight in the mixed fuel.
．． 8% by weight, the upper limit being purely for economic reasons.

According to the invention, when forming the dispersion of additives, pulverized coal, oil and optionally water, any temperature may be employed, for example from 50 to 120 "C"'? :: The mixing pressure may be elevated pressure, normal pressure, or reduced pressure degassing, and the stirrer and stirring conditions are not restricted.

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.

Example A homo mixer equipped with a stirring spring for high viscosity produced by Tokushu Kika Kogyo was used as a small-scale model of the stirring section of the COM manufacturing apparatus, and an ash adhesion prevention test was conducted as follows.

Add the additives (shown in Table 2) of COM (properties shown in Table 1) heated to 90°C, pre-mix with a spatula, and then mix at the same temperature of 5000 rpm. de1
Stir for 0 minutes. Subsequently, after cleaning the COM adhering to the stirrer with a solvent, the amount of ash firmly adhering around the rotating parts was determined. It can be said that the lower the ash content, the better the ash adhesion prevention properties.

In addition, the 00M stability test was conducted using the following COM (first
0.15% of the additive was added to (the properties are shown in the table) and stirred for 4 minutes with a homomixer at 4000 rpm.

The stirred COM is placed in a 500-ml polyethylene bottle and left in a thermostat at 64°C for 10 days. Leave to stand (wheat, turn the plastic bottle upside down and take out the COM. At this time, measure the weight of the COM remaining at the bottom of the plastic bottle and the coal concentration.

The results are shown in [Table 3].

(Margin below) [Table 1] Characteristics of COM The abbreviations in [Table 2] indicate the following structures.

EO: -CH2-CH2-0-Co: -(C11
2)? CI! 3C) 13 C9: -(
Hz) sct13PO: -CI+2-CH-0-C
10: -(CH2)11c113CI13
CIa: -(CH2) Lending C113BO: -CI
(2 C)12 C2: -C11zCHa -C)I-0- C4: (CH2)3 H3

Claims (1)

[Claims] (A) Amines, phenols, and formaldehyde used to improve the stability of a pulverized coal-oil mixture, disperse ash separated from pulverized coal, and prevent ash from adhering to various equipment. A compound obtained by adding an alkylene oxide to the reaction condensate of
R_3: an alkyl group or acyl group having 1 to 30 carbon atoms or a hydrogen atom, R_2: an alkylene group having 2 to 6 carbon atoms, n=1 to 20) A fine powder characterized by containing a polyamine as an essential component. Additive for coal-oil mixtures.