JPS63165488A - Additive for powdered coal-oil mixture - Google Patents

Abstract

PURPOSE:To obtain an additive improving stability of a powdered coal-oil mixture, by dispersing ash separated from powdered coal and preventing the ash from attaching itself to various devices, containing a specific polyether and a specific polyamine as essential components. CONSTITUTION:The aimed additive containing (A) a polyether which consists of a polyoxyalkylene alkyl phenyl ether formalin condensate and has 300-100,000 molecular weight and (B) a polyamine shown by formula (R1 and R3 are 1-30C alkyl, acyl or H; R2 is 2-6C alkylene; n is 1-20) in a blending ratio of the component A/B=95/5-5/95 (preferably 90/10-50/50) as essential components. A polyoxyalkylene octyl (nonyl or dodecyl) phenyl ether formalin condensate (2-10 nucleus compound) may be cited as the component A and amidated coconut fat and oil fatty acid or amidated beef tallow fatty acid as the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 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.

Conventionally, COM had a problem due to sedimentation of coal particles, but this problem was solved with the invention of an excellent stabilizer, and it is already being produced in large quantities and used for combustion as an alternative fuel to petroleum for electric power.

However, the ash contained in 00M is
It adheres to places where strong mixing and agitation occurs, such as M pumps, control valves, and piping elbows, or where the flow rate changes suddenly, making it necessary to frequently stop the line and scrape it off or clean it, creating new problems. It has been occurring. Also, patent number 127
The C0M stability of the phenols shown in 8758 and 13013345 was still insufficient, and ash adhesion occurred.

Therefore, there has been a strong desire to develop additives that further improve the stability of COM and prevent ash adhesion.

As a result of extensive research into additives that maintain long-term stability and prevent ash adhesion, the present inventors have developed a specific additive that uses specific alkylphenols as a starting material and adds fullkylene oxide to it. It has been found that additives containing polyether compounds with molecular weight and polyamines or derivatives thereof are very effective.

By using the additive of the present invention, a COM with better stability and no ash adhesion than before can be obtained.

Not only can COM be stored in tanks for a long period of time, but there is no ash adhesion to various equipment such as COM pumps and control valves, making mass production and combustion possible.

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 the type or production area, as well as regardless of chemical composition or moisture content.

Such coal is put into oil as it is or after being crushed,
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 reduces the It's even better because it prevents spontaneous combustion and dust.

Moisture in the coal may be removed during dry pulverization, or may be crushed during or after wet pulverization, and there is no problem even if coal containing low moisture is not removed.

The particle size of pulverized coal is usually an average particle size of 2, judging from combustibility.
00 microns or less is preferable, and even smaller particle sizes of 100 microns or less are preferable, but as far as physical properties such as stability of COM are concerned, there is no problem even with larger particle sizes.The content of this fine powder is determined by the final It is 20 to 70% by weight based on the 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. This is not preferred because the benefits of

Therefore, it can be contained in 20 to 70% by weight, but 30 to 8% by weight can be contained.
0% by weight is more preferred.

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, various blended oils, etc.1 For example, gas station waste oil (automobile lubricating oil).

(cleaning oil), ironworks waste oil (machine oil, cutting oil, cleaning oil, and mixtures thereof) 1 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.
Even if OM is prepared, COM may be made from a single oil (preferably petroleum crude oil 1 heavy oil) and then other oils may be mixed or co-fired.

Water is caused by water contained in coal mixed into 00M,
There are cases where the manufacturer or user adds water, but transportation costs, storage costs, and other general and administrative costs will increase depending on 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 water has the property of improving the stability of COM and the effect of reducing NOx and vizine in exhaust gas during combustion, a small amount of water is allowed. Therefore, the total water content is preferably 15% by weight or less, preferably 8% by weight or less, and may not be contained at all.

The additive for pulverized coal-oil mixtures according to the present invention is a polyether having a molecular weight of 300 to 100,000 made of a polyoxyalkylene alkylphenyl ether formalin condensate, and further has the general formula % (Rs * Rs: carbon number 1 It is characterized by containing as an essential component a polyamine represented by ~30 alkyl groups or acyl groups or hydrogen atoms, R2: a fullylene group having 2 to 8 carbon atoms, n = 1 to 20).

The polyether referred to herein is a residue of the above-mentioned starting material having the general formula 2. R is a fullylene oxide such as ethylene, propylene, butylene, and n is a number determined by the degree of polymerization.

m is the number of active hydrogens that Z has, and is 2 to 20, preferably 2 to 10. RO may be a single alkylene oxide or two or more types, and the arrangement order remains independent.
May be block copolymerization type, random copolymerization type,
However, in the case of a copolymer type surfactant, it is generally preferable to use a block copolymer type.

Next, the starting material corresponding to Z is obtained by condensing an alkylphenol with formaldehyde to obtain 2 to 20 nuclei, preferably 2 to 1
0 nuclear body. The alkylphenol referred to herein is preferably octylphenol, nonylphenol, dodecylphenol, or the like.

The polyether of the present invention can be obtained as described above, but in addition to the above, it is also possible to add-polymerize fullylene oxide to alkylphenol and then condense it with formaldehyde, and the synthesis method is not particularly limited.

Next, the general formula % formula % (Rs, Rs: 'fR prime number 1 to 30 alkyl group or acyl group or hydrogen atom, R2: carbon number 2 to e
The polyamine represented by a fullylene group (n=1 to 20) is a polyamine alone or a derivative thereof such as ethylene diamine, beef tallow propylene diamine, triethylene tetramine, tetraethylene pentamine, and pentaethylene hexane. ! i derivatives are reaction products with alkyl halides 1 such as dodecylpropyne diamine.

These include dodecyltriethylenetetramine, tallow dipropylenetriamine, etc.

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

The blending ratio of polyether (A) and polyamine (B) of the present invention is A/B 3515 to 5/85. Preferably 9G/
10-50150.

In order to stabilize COM and exhibit the ash adhesion prevention effect using the additive of the present invention, the additive must be added after dry-pulverized pulverized coal is mixed into oil, or the additive must be dissolved in oil in advance and then dry-pulverized. You can either add crushed pulverized coal or mix the pulverized coal, oil and additives all at once, and water may be added to each of them.In the case of wet pulverization, the It may be added at any time during or after grinding, and in this case, water may also be added.

The amount of the additive of the present invention added to the mixed fuel system varies depending on the coal type, coal particle size distribution, and oil type, but is generally 0.01 to 5% by weight in the mixed fuel.

Preferably it is between 0.04 and 0.8% by weight, the upper limit being due solely to 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. The stirrer and stirring conditions are not limited as long as the effect of the additive is not inhibited, but strong stirring at a circumferential speed of 2 m/sec or more is particularly preferred.

Next, the present invention will be explained in more detail with reference to examples.

Example (1) As a small-scale model of the stirring section of the 00M manufacturing equipment, a homo mixer equipped with a stirring spring for high viscosity manufactured by Tokushu Kika Kogyo 2 was used, and an ash adhesion prevention test was conducted as follows.

The additive of the present invention was added to COM heated to 80°C, premixed with a spatula, and then heated to 500°C at the same temperature.
Stir for 10 minutes at 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.

Moreover, the C0M stability test was conducted by a rod penetration test.

The test device was a stainless steel cylinder with an inner diameter of 5.5C and a height of 20C+S, with a distance of 80cm and 12cm from the bottom.
Use one that has an outlet with a stopper at each position. Pour the specified mixed fuel into this cylinder to a height of 18cm from the bottom, remove the stopcock at 12cm from the bottom, and then remove the stopcock at 12cm from the bottom.
Take out the COM) in the cylinder at cg+,
The viscosity and coal concentration were measured using the upper layer sample. Next, the stopcock at the 8c position was removed from the bottom, and the mixed fuel above was taken, and its viscosity and coal concentration were measured as the middle layer sample. Finally, remove the bottom stopper and remove the remaining COM.
The viscosity and coal concentration of the lower layer samples were measured. Note that all measurements of viscosity were performed at 70°C.

Table 1 shows the additives used in this example.

Furthermore, Table 2 shows the ash adhesion prevention rate and stability evaluation results.

From Table 2, the phenol-formalin condensate (ternary) EO adduct shown in Comparative Example and Additive (1) did not have sufficient C0M stability and did not have an ash adhesion prevention effect.

On the other hand, when the additives (A-G) of the present invention are used, sufficient CO
M stability was obtained, and the ash adhesion prevention rate was 80 to 99%, and in particular, amidated products of coconut oil fatty acid and beef tallow fatty acid showed excellent stability and ash adhesion prevention effect.

Example (2) An ash adhesion prevention test using an actual COM manufacturing device (1 t/h) was conducted as follows.

No. 1 when manufacturing COM using Australian bituminous coal and Middle East C heavy oil.
Nonylphenol formalin condensate trinuclear body EO shown in the table
Adduct (average molecular weight 1000) and amidation product of palm fatty acid and tetraethylenepentamine (1:1) 85/15
They were used in combination at a blending ratio of , added to COM before the line mixer, and operated for 30 days.

As a result, the stirrer, C0M pump, control valve.

It was confirmed that no ash adhesion occurred to the elbows of piping, etc., and that a stable COM with excellent ash adhesion prevention effect was obtained.

Procedural amendment

Claims (1)

[Claims] 1. Polyoxyalkylene alkylphenyl used to improve the stability of pulverized coal-oil mixture, disperse ash separated from pulverized coal, and prevent ash from adhering to various equipment. Molecular weight 300-1 consisting of ether-formalin condensate
00,000 polyether and further (2) general formula R_1-NH-(R_2NH)n-R_3 (R_1, R_3: alkyl group or acyl group or hydrogen atom having 1 to 30 carbon atoms, R_2: carbon number 2 to 6 Additive for pulverized coal-oil mixture 2, characterized in that it contains as an essential component a polyamine represented by an alkylene group, n=1 to 20), wherein the polyoxyalkylene alkylphenyl ether formalin condensate is polyoxyalkylene octyl Phenyl ether formalin condensate (2-10 nuclear bodies), polyoxyalkylene nonyl phenyl ether formalin condensate (2-10 nuclear bodies), or polyoxyalkylene dodecyl phenyl ether formalin condensate (2-10 nuclear bodies), and The additive for pulverized coal-oil mixtures according to claim 1, wherein the polyamine is an amidated product of coconut oil fatty acid or beef tallow fatty acid.