JPS63254194A - Additive for pulverized coal-oil mixture - Google Patents

Abstract

PURPOSE:To obtain an additive providing a pulverized coal-oil mixture having excellent stability and fluidity, comprising a compound obtained by reacting a terminal hydroxyl group of a specific polyether compound with an epoxy- containing compound as a main component. CONSTITUTION:(A) A polyether compound having 1,000-100,000 (preferably 3,000-100,000) is blended with (B) an epoxy group-containing compound such as functional group-containing glycidyl compound or glycidyltrimethylammonium chloride, heated at 40-150 deg.C (preferably 50-120 deg.C) and optionally by the use of an acid or base catalyst to react at least part of terminal hydroxyl group of the component A with the component B. The prepared compound is used as a main component to give the aimed additive. Usually 0.01-5wt.% (preferably 0.04-0.8wt.%) additive is added to a mixed fuel.

Description

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

Conventionally, although pulverized coal has a low price per calorific value, it has disadvantages such as difficulty in transportation, difficulty in controlling combustion, low calorific value, and large storage space. However, there was a problem with the fuel. COM does not have the above drawbacks and has a lower price per calorific value than oil alone, so its practical value of 4 tr is high. However, if pulverized coal and oil are simply mixed together, the pulverized coal particles will settle and separate due to the difference in specific gravity.

Satisfactory COM cannot be obtained because it condenses and loses fluidity.

Therefore, the inventors of the present invention have continued intensive research into additives that can maintain long-term stability and fluidity and adjust more economical COM, and as a result, have come to provide the present invention. It is something. That is, the main component is a compound obtained by reacting a portion or all of the terminal hydroxyl groups of a polyether compound with a molecular weight of 1,000 to 100,000, preferably 3,000 to 100,000, with an epoxy group-containing compound. This is an additive for pulverized coal-oil mixtures characterized by:

As the stone used for COH, various coals such as anthracite, bituminous coal, sub-bituminous coal, and 7B coal can be used.
II' Any material can be used, regardless of its base, chemical composition, or moisture content.

Such coal is put into oil as it is or after being crushed,
It may be directly pulverized in oil using various wet pulverizers, or it may be made into pulverized coal using a conventional dry pulverizer. However, wet pulverization υ: is even better because it improves the stability of COH and prevents spontaneous combustion and dust during pulverization. Moisture in the coal may be removed during dry pulverization, or may be removed during or after wet pulverization, and there is no problem even if coal containing only a small amount of moisture is not removed. The particle size of pulverized coal is usually preferably 200 microns or less in average particle size judging from combustibility, and even smaller particle sizes of 100 microns or less are preferred, but as far as physical properties such as COH stability are concerned, it is preferable to 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 increase and fluidity will be lost, which is undesirable. The following cases are not preferable because the economic advantages associated with the inclusion of pulverized coal are reduced. Therefore, it can be contained in 20 to 70%, but 3
More preferably 0 to 60% by weight.

In addition, the oil used for COM is 1 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 used as fuel for -IIQ, such as heavy oil caps, ethyl L/N cracked residual oil, creosote oil, anthracene oil, various blended oils, etc. ), Ironworks waste oil (machine oil, cutting oil, washing oil, and mixtures thereof) 1. Waste oil from oil tankers and other ships, − grade chemical factory waste oil, etc., and also includes mixtures of these. Alternatively, COM may be adjusted using pre-blended oil, or CON may be prepared using a single oil (preferably petroleum crude oil or heavy oil) and then mixed or co-fired with oil.

Water is caused by water contained in 1 coal mixed into C0M,
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 is undesirable that the heat of evaporation during combustion is lost and the loss of heat IO becomes large, so the smaller the amount, the better.

- On the other hand, since water has the property of improving the stability of COM and has the effect of reducing NOx and vizine in the exhaust gas during combustion, the mixing of small items is allowed. Therefore, the entire book branch is 1
5 weight% or less, preferably 6 weight% or less, and may not be contained at all. Next, the polyether compound with molecule Ql, 000 to 100,000 is ・A2 formula Z ((RO)nH
)m A peroxide (radical generating catalyst) that forms intramolecular or intermolecular bonds, has at least one hydroxyl group in the molecule, and has a molecular weight of 1,00ON1.
00,000, preferably 3,000 to 100,000.

These polyether compounds are produced by using at least one of various alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, etc., as starting materials, and generally by using a catalyst such as an alkali or acid under pressure. It is obtained by addition polymerization using a block copolymerization type or a random copolymerization type.

The starting materials for such polyether compounds include various substances having active hydrogen.

Various substances containing active hydrogen include, for example, active hydrogen containing 1 to 1
Alcohols with 4 active hydrogens, alcohols with 5 active hydrogens, amines with 1 to 4 active hydrogens, amines with 5 or more active hydrogens, carboxylic acids with 1 to 4 active hydrogens, active hydrogens Carboxylic acids, phenols, naphthols, phenols, or naphthols having 5 or more hydrogen atoms, or formalin condensates with other aromatic compounds, etc., and include carboxyl groups, amino groups,
Hydroxic acid 7! It has different kinds of active hydrogens in the same molecule.

Next, the binders that form intramolecular or single-layer bonds include polyvalent (2 or more active hydrogen) carboxylic acids, polyvalent carbonyl alcohols, polyvalent epoxy compounds, polyvalent aldehydes, and polyvalent incyanates. The peroxide (radical generating catalyst) that causes intramolecular or intermolecular bonding is a known iM oxide that generates radicals.

Next, part or all of the terminal hydroxyl of the specific polyether compound is reacted with the epoxy compound containing the epoxy compound.

The epoxy group-containing compound is, for example, an olefin oxide, an internal olefin oxide, a thuringyl etherified product of a -valent or polyvalent aliphatic alcohol, a glycidyl etherified product of a -valent or polyvalent alicyclic alcohol, a -valent or Glycidyl etherified products of polyvalent aromatic alcohols, -cricidylaminated products of -valent or polyvalent aliphatic amines, glycidyl aminated products of -valent or polyvalent alicyclic amines, -valent or polyvalent aromatic amines Glycidyl aminated products of , glycidyl etherified products of Fe and nols,
Glycidyl ether compounds of polyhydric phenols
Examples include glycidylated products containing a functional group represented by CH2X\1 (X is a hydroxyl group, an amine group, an allyl group, an acryloyl group, or a methacryloyl group), glycidyltrimethylammonium chloride, and the like. These reaction conditions include mixing the epoxy compound and polyether compound, heating at 40 to 150°C.
The object can be achieved by heating preferably at a temperature in the range of 50 to 120°C and carrying out a reaction. In this case, if necessary, use regular acid or J1! The solution is to use a base catalyst.

In the present invention, a compound obtained by reacting part or all of the terminal hydroxyl group of a specific polyether compound with an epoxy group-containing compound is used as a COM additive (hereinafter referred to as an additive).

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

Further, the additive of the present invention can of course be used alone or in a mixture of the additives of the present invention, but it may also be used in combination with one type or multiple types of other drugs.

In order to stabilize and fluidize CON using the additives of the present invention, the additives can be added after dry-pulverized pulverized coal is mixed in oil, or the additives can be dissolved in oil and then pulverized by rotary pulverization. It is sufficient to add charcoal or to mix together the three groups of pulverized coal, oil and additives, and water may be added to each separately.In the case of wet pulverization, the pulverized charcoal, oil and additives may be mixed together. ,
Alternatively, it may be added at any time after pulverization. In this case too, water may be added.

The amount of the additive of the present invention added to a mixed fuel system varies slightly depending on the type of coal, coal particle size distribution, and oil type, but in general, the amount of the additive of the present invention added to the mixed fuel is 0. O1-5% by weight, preferably 0.04-5% by weight
0.8%, and the 1st limit is simply due to economic reasons.

According to the present invention, additives, pulverized coal, oil and, if necessary,
When forming a dispersion system consisting of water, any temperature is adopted, for example, mixing at 50 to 120°C, and the mixing pressure is pressurized,
Normal pressure, reduced pressure deaeration, etc. may be used, and the stirrer and stirring conditions are as follows:
No commitment is made unless the action of the additive is inhibited, but
In particular, strong stirring at a circumferential speed of 2 m/sec or more is preferred.

By using the additive of the present invention, a COW with significantly improved stability and fluidity than before can be obtained, and it can be used not only at room temperature but also at room temperature.
Even when stored at high temperatures for long periods of time, there is almost no pulverized sedimentation, and even if a small amount of sedimentation occurs, due to the excellent action of the additives of the present invention, there is almost no agglomeration of the settled pulverized coal, so it can be easily stirred. It can be reflowed only with water. Of course, stirring is not necessary for a short period of time (about 15 stitches).

This has made it possible to safely transport CON in tankers over long periods of time, store it in tanks, and transport it through pipelines and piping. In addition, the additive of the present invention can be used in a smaller amount than conventional additives, and can further promote the practical use of GOH from an economic standpoint.

Next, the present invention will be explained in more detail with reference to Examples. In the examples, "%" is based on the electric resistance welding standard. The rod penetration test shown in the examples was conducted as follows. The test device used is a stainless steel cylinder with an inner diameter of 5.5 mm and a height of 20 cm, which has an outlet with a stopper at the bottom, 6 cm from the bottom, and 12 cm from the bottom. Fill this cylinder with the specified mixed fuel to a height of 18 cm from the bottom, cover the top of the cylinder with a lid with a guide hole in the center, and pass a smooth glass forest with a diameter of 5 cm at the tip (all sides) through the center guide hole. (20 g) was dropped vertically, and the distance from when the tip entered the mixed fuel until it reached the bottom of the cylinder was measured, and this distance was taken as the rod penetration time.

The shorter the gap, the less sedimentation and consolidation of the pulverized coal, resulting in a mixed fuel with excellent fluidity.

After the test, the 12 cm stopper was removed from the bottom, and the mixed fuel above it (i.e., the mixed fuel in the cylinder 12 to 18 cm 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 6CI11 position was removed from the bottom, and the mixed fuel above it was sampled, and its viscosity and coal concentration were measured as a middle layer sample. Finally, the bottom stopper was removed, the remaining mixed fuel was collected, and its viscosity and coal concentration were measured as a lower layer sample.

The forest penetration test and viscosity measurement described above were both carried out at 70
It was carried out at a temperature of °C.

Table 1 shows the additives of the invention used in the examples.

Table 2 shows the stability test results of GOH using the additives shown in Table 1 and comparative products.

As shown in Table 2, when the additive of the present invention is used, 70
Even after standing at ℃ for 30 days, the forest penetration time is as short as 1.0 to 5.0 seconds, and there is almost no difference in viscosity or coal concentration between the upper, middle, and lower layers, resulting in a homogeneous and stable COM. It was confirmed.

Claims (1)

[Claims] Molecular weight 1,000 to 100,000, preferably 3,000 to 1
An additive for a pulverized coal-oil mixture, characterized in that the main component is a compound obtained by reacting some or all of the terminal hydroxyl groups of a polyether compound with an epoxy group-containing compound.