JPH01318084A - Additive for pulverized coal/oil mixture - Google Patents

Abstract

PURPOSE:To obtain an additive which can improve the stability and flow of a pulverized coal/oil mixture by using a specified polyether compound as an effective component. CONSTITUTION:A reaction product of a polyamine (a) of 2-6 N atoms (e.g., ethylenediamine) with at least one member (b) selected from among an aldehyde and a ketone (i), an alkyl halide (ii), an isocyanate (iii), an active double bond- containing compound (iv) and an epoxy compound (v) (e.g., chlorooctane) and an alkylene oxide (c) (e.g., ethylene oxide) are subjected to an addition reaction to obtain a polyether compound (A) of an MW of 1000-200000, containing 3-80wt.%, desirably, 6-50wt.% ethylene oxide as component (c). At least one component A is optionally dissolved in a solvent (B) (e.g., isopropyl alcohol) to obtain the title additive. 0.01-5wt.% said additive is added to a mixture comprising pulverized coal, an oil and, optionally, water.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an additive for producing a pulverized coal-oil mixture (hereinafter referred to as rcOMJ) having excellent stability and fluidity.

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 as a fuel. COM does not have the above-mentioned drawbacks and has a lower price per calorific value than oil alone, so its practical cost is high. However, if pulverized coal and oil are simply mixed, a satisfactory COM cannot be obtained because the pulverized coal particles settle and separate due to the difference in specific gravity, coagulate, and lose fluidity.

Therefore, the present inventors continued intensive research on additives to maintain long-term stability and fluidity and to prepare more economical COM, and as a result, we developed a polyether compound shown in JP-A-57-165490. I ended up inventing it.

However, these conventional polyether compounds have a large number of side chains in one molecule and have a complex or cylindrical structure. In order to bring out the effects, it was necessary to apply a strong amount of energy to the mixture.

However, when manufacturing COM, it is essential to manufacture it at a low cost, and with regard to mixing, it is necessary to obtain sufficient stability with as low power as possible.

This invention was made by focusing on such conventional problems.In other words, it is possible to achieve stability that could not be achieved conventionally, not only under strong agitation but also under low agitation. We have succeeded in developing an innovative additive that can produce COM.

Specifically, (1) polyamines having 2 to 6 nitrogen atoms and the following (a) to +1143 fat aldehydes, ketones (bl alkyl halides (c) isocyanates, thioisocyanates (dl
An additive whose essential component is a polyether compound obtained by adding alkylene oxide to the reacted active double bond metal compound or fe]epoxy compound to have a molecular weight of 1,000 to 200,000. It is.

It is thought that the reason why the additive of the present application exhibits an excellent effect is that by adding a modification operation to the polyamine, the hydrophobicity is increased and the dispersion speed in oil is accelerated.

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, production area, 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 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. Judging from combustibility, the particle size of pulverized coal is usually preferably 200 microns or less in average particle size, and even smaller particle size 100 microns or less, but as far as physical properties such as COM stability are concerned, the particle size may be even smaller. There is no problem even if it is large. 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 become extremely high and fluidity will be lost, which is undesirable. In this case, the economic advantages associated with the inclusion of pulverized coal are reduced, which is not preferable. Therefore, the content can be 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, A heavy oil, B heavy oil, C
Oils and waste oils commonly used as fuel such as heavy oil, ethylene decomposition residual oil, creosole oil, anthracene oil, various blended oils, etc., such as gas station waste oil (automobile lubricating oil, cleaning oil), ironworks waste oil (machine oil, cutting oil, cleaning oil and mixed oil), waste oil from oil tankers and other ships, -
Refers to general chemical factory waste oil, etc., and also includes mutual mixtures thereof. Among them, it is preferable to use petroleum crude oil, B heavy oil, and C heavy oil. The COM may be prepared using only a single oil or a pre-blended oil, or the COM made from a single oil (preferably petroleum crude oil or heavy oil) 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 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 6% by weight or less, and may not be contained at all.

1 The additive for pulverized coal-oil mixture used in the present invention uses a polyamine derivative having 2 to 6 nitrogen atoms as a starting material,
Add alkylene oxide to this, and its molecular weight is 100.
It is characterized by containing a polyether compound with a concentration of 0 to 200,000 as an essential component.

The polyether compound contains ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. as alkylene oxide, and in particular, the content of ethylene oxide is 3 to 80% based on the polyether compound.
% by weight, preferably from 5 to 50% by weight.

The polyamine derivatives referred to herein are those obtained by reacting polyamines having 2 to 6 nitrogen atoms, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, or mixtures thereof, with the compounds shown below. It is.

(a) Aldehydes, ketones An example of aldehydes is formaldehyde.

Aliphatic aldehydes such as acetaldehyde, butyraldehyde, isobutyraldehyde, capryaldehyde, lauric aldehyde, stearaldehyde, aliphatic dialdehydes such as glyoxal and succindialdehyde, and benzaldehyde.

Examples include aromatic aldehydes such as salicylaldehyde and α-naphthaldehyde.

Examples of ketones include aliphatic ketones such as acetone, ethyl methyl ketone, methyl vinyl ketone, methyl isobutyl ketone, and diisopropyl ketone, alicyclic ketones such as cyclopentanone and cyclohexanone, acetophenone, propiophenone, and benzophenone. , 2-acetonaphthone, and other aromatic ketones.

(b) Alkyl halide Alkyl halide is generally represented by 2CnH2h47X [C: carbon H: hydrogen X: halogen n is an integer from 1 to 30], and the alkyl group includes ethyl, propyl, isobutyl, tert-butyl, octyl. , nonyl,
Examples of halogens combined with decyl groups include fluorine, chlorine, bromine, and iodine, and the combination is not particularly limited.

tC) Isocyanates Examples of isocyanates include methyl isocyanate,
Monoisocyanates such as ethyl isocyanate, butyl isocyanate, carbanyl, and naphthyl isocyanate, and polyvalent diisocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, metaxylene diisocyanate, 1,5-naphthylene diisocyanate, and 4.4' diphenylmethane diisocyanate. Examples include isocyanates.

(dl Things with active double bonds Examples of things with active double bonds include ethylene, propylene, butene, butadiene, diisobutylene, styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, etc., acrylic acid, methacrylic acid, acids, carboxylic acids such as crotonic acid, fumaric acid, maleic acid, and itaconic acid, or their esters, acrylamide, and methacrylamide.

Examples include N,N-dimethylacrylamide.

(e) Epoxy compound Epoxy compounds include glycidol, allyl glycidyl ether, and butyl glycidyl ether.

Examples include glycidyl compounds such as phenylglycidyl ether, butylphenylglycidyl ether, and nonylphenylglycidyl ether.

In short, the compounds shown in (a) to (e) have 2 nitrogen atoms.
The starting material is reacted with ~6 polyamines.

The alkylene oxide added thereto includes ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and the like.

In the case of copolymerization, block copolymerization or random copolymerization may be used, and either one may be added first, but
In order to effectively exhibit surface active ability, block copolymerization is more preferable.

When the alkylene oxide is added, the molecular weight of the resulting polyether compound is 1,000 to 200,000, preferably 2,000.
The ratio is ~100,000. Further, the polyether compound contains ethylene oxide as an alkylene oxide, and the content thereof is 3 to 80% by weight of the polyether compound,
Preferably it is 5 to 50% by weight, which provides even better performance.

The additive of the present invention may be used as it is, or may be used after being dissolved in a solvent such as isopropyl alcohol, butyl cellosolve, or petroleum distillate.

Furthermore, it is of course possible to use the additive of the present invention alone or as a mixture of the drugs of the present invention, but it may also be used in combination with one type or multiple types of other drugs.

To stabilize COM using the additive of the present invention, either dry-pulverized pulverized coal is mixed into oil and then the additive is added, or the additive is dissolved in oil beforehand and then dry-pulverized pulverized coal is added. Alternatively, the pulverized coal, oil and additives may be mixed all at once, and water may be added to each of them. Alternatively, 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 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,
It may be degassed under normal pressure or reduced pressure, and the stirrer and stirring conditions are not particularly limited.

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 1 The C0M stability test shown in the Examples was conducted as follows.

First, the COM was adjusted by low stirring at a circumferential speed of 1 m/sec.

Next, as a test device, inner diameter 5.5G height 20c +++
Stainless steel cylinder, 6CI11 from the bottom.
．． Use one that has an outlet with a stopper at each position of 12 cm. Fill the cylinder with the specified mixed fuel to a height of 13cn+ from the bottom, remove the stopcock 12cm from the bottom, and remove the COM above it (i.e., the COM in the cylinder at a height of 12 to 18cm from the bottom). was taken out and used as an upper layer sample, and its viscosity and coal concentration were measured. Next, the stopcock at the 6G position 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 COM was collected, and its viscosity and coal concentration were measured as a lower layer sample. Note that all measurements of viscosity were performed at 70°C.

Table 1 shows the additives used in this example. Also, the second
The table shows the stability test results of C0M with the additives shown in Table 1.

As shown in Table 2, when using the additive of the present invention, 70℃
Even after standing still for 3 days, there was almost no difference in the viscosity and coal concentration of the upper, middle, and lower layers (it was confirmed that a homogeneous and stable COM was obtained.

Claims (2)

[Claims] (1) Reacting a polyamine having 2 to 6 nitrogen atoms with (a) aldehydes, ketones, (b) alkyl halides, (c) isocyanates, (d) active double bond-containing substances, or (e) epoxy compounds. An additive for a pulverized coal-oil mixture, characterized in that it contains as an essential component a polyether compound obtained by adding an alkylene oxide to the starting material and having a molecular weight of 1,000 to 200,000. (2) Claim 1, wherein the polyether compound contains ethylene oxide as an alkylene oxide, and the content thereof is 3 to 80% by weight, preferably 5 to 50% by weight, based on the polyether compound. Additive for pulverized coal-oil mixtures as described.