JPS6079094A - Additive for coal/oil mixture - Google Patents

Abstract

PURPOSE:To provide an additive for coal/oil mixture which contains as effective ingredient a specified high molecular weight polyol obtained by a specified reaction, has a low viscosity and a high fluidity within a wide range of concn. and is capable of controlling sedimentation of coal particles over a long period. CONSTITUTION:The additive contains as effective ingredient a polyether polyol having an M.W. of 100,000-2,000,000 or deriv. thereof (e.g. reaction product of polyether polyol with epihalohydrin) obtained by adding 3C or higher alkylene oxide (e.g. propylene oxide) to a polyamine having an M.W. of 10,000-200,000 or modified product thereof (e.g. polyethyleneimine). The additive has polyamine as hydrophilic segment and alkylene oxide structure as hydrophobic segment, and hydrophilic or hydrophobic group at the terminal is negligibly small as compared with the size of molecule. Thus the additive imparts excellent dispersion stability and a low viscosity to a coal/oil mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an additive for a coal-oil mixed fuel that has excellent dispersion stability, is low in viscosity, and can be used to produce a mixed fuel of pulverized coal and fuel oil.

Many methods have been investigated to treat coal like a fluid. A relatively simple method of coal fluidization technology is coal-oil mixed fuel (coal-oil mixed fuel) in which finely powdered coal is dispersed in fuel oil.
Hereinafter, it will be abbreviated as 00M. )It has been known. In order to produce OOM, from an economic point of view, it is necessary to make the concentration of cheap coal as high as possible, and from a technical point of view, it must be possible to handle it on the same level as oil, that is, it must have low viscosity, good fluidity, and be dispersed in oil. It is important that the coal particles do not settle and have good stability.

Generally, when the concentration of coal increases, the viscosity increases significantly and fluidity is lost, and when the concentration of coal decreases, economic efficiency and dispersion stability decrease.

There are methods to increase the coal concentration by coarsening the particle size of coal particles to suppress an increase in viscosity and to increase the handling temperature, but all of these methods promote sedimentation of coal particles and reduce dispersion stability. There is also a method of pulverizing coal into ultra-fine particles, but although this method improves dispersion stability, it increases viscosity, forcing the coal concentration to be lowered, and the amount of power required for pulverization increases significantly. Significantly less practical.

Methods of using additives to solve the above problems have been investigated, and many additives have been proposed. Among these additives, polyether compounds with polyoxyalkylene oxide chains have a carbonization degree of 1 and the surface properties of coal (ionic).

It exhibits relatively good performance because it is not affected by the degree of porosity or the like.

However, when polyether compounds are used as additives, O
When producing OM, there is a drawback that when the coal concentration exceeds 50% by weight, the viscosity increases significantly and fluidity is lost.

The object of the present invention is to provide a fuel oil mixture suitable for producing a mixed fuel of pulverized coal and fuel oil, which has excellent fluidity over a wide concentration range, has low viscosity, and suppresses sedimentation of coal particles over a long period of time.
We provide additives for OM.

The active ingredient of the present invention is a polyether polyol or a derivative thereof having a molecular weight of 100,000 to 2,000,000, which is obtained by adding an alkylene oxide having 3 or more carbon atoms to a polyamine having a molecular weight of 10,000 to 200,000 or a modified product thereof. The present invention provides additives for cOM.

The polyamine or its modified product used for producing the polyether polyol or its derivative used in the present invention has a molecule t of 10,000 to 200,000, preferably 10,000 to 10
Ten thousand. Such a compound is easily available as a polymer of ethyleneimine, but in the present invention, it is not limited to polyethyleneimine, but at least 50 or more, usually 100 or more, and particularly preferably 200 or more are bonded to the nitrogen atom. Any polyamine having an active hydrogen of 10% can be used without any restrictions. The polyethyleneimine may be an ethyleneimine addition polymer of an active hydrogen compound such as an alcohol, an amine or a thiol, an ethyleneimine addition polymer using an acidic catalyst, or a polyethyleneimine. In the present invention, a polyamine in which a part of the active hydrogen is modified with a suitable modifier can also be used. Examples of the modifier include alkylating agents such as alkyl halides and alkyl sulfates, amidizing agents such as carboxylic acids, carboxylic acid anhydrides, and carboxylic acid halides, glycidyl compounds, and other modifiers.

An example of a glycidyl compound is glycidol.

Allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, 2-methyl glycidyl ether, etc. are mentioned. The polyamine used at this time is selected so that the molecule 11X after modification is within the range of 10,000 to 20,000.

Ru. Polyamines or modified products thereof are involved in the formation of branched molecules of polyketyl polyols or derivatives thereof, and act as hydrophilic groups, so they are highly water-soluble or hydrophilic.

If the molecular weight of the polyamine or its modified product is less than 10,000, the number of branched chains in the molecule will be small and the proportion of hydrophilic groups in the molecule will be small, so the dispersion stability of OOM will be insufficient. However, it has the disadvantage of high viscosity. -If it is larger than 200,000, the ratio of hydrophilic groups will become large or the molecular weight will become too large, so 0.
0M has disadvantages of insufficient dispersion stability or high viscosity.

The polyether polyol or its derivative used in the present invention has 3 carbon atoms in the above-mentioned polyamine or its modified product.
A polyether polyol obtained by adding the above alkylene oxide, or a derivative obtained by optionally modifying the polyether polyol with an appropriate reaction reagent, and has a molecular weight of 100,000 to 2 million, preferably 100,000. ~1
500,000, more preferably in the range of 150,000 to 1,000,000. If the molecular weight is smaller than this range, the stability of OOM will be insufficient, while if it is larger, the viscosity of 00M will become extremely high, so either case is unsuitable. The alkylene oxide having 3 or more carbon atoms to be added to the polyamine or its modified product is propylene oxide.

Examples include butylene oxide, cyclohexene oxide, a-olefin oxide having 6 to 20 carbon atoms, and
Alkylene oxides of No. 4 are preferably used. When this polyether polyol or its derivative contains a polyoxyethylene structure in its molecule, it is difficult to obtain a low viscosity OOM. Therefore, it is desirable that the molecule contains substantially no polyoxyethylene structure. Therefore, when introducing an oxyethylene structure into the molecule, it is preferable to add ethylene oxide before adding the alkylene oxide having 3 or more carbon atoms, and the ratio thereof is 5 weight coefficients or less of the molecular weight of the polyether polyol. In particular, it should be less than 3 weight. In addition, if the polyether polyol or its derivative has too high hydrophilicity, the dispersion stability of OOM will not improve, and the separation and sedimentation of coal particles will not be possible with cows. The molecular weight of the modified product is 50 dl of the molecular weight of the polyether or its derivative)
It is preferably less than 7.

Examples of the polyether polyol derivatives used in the present invention include the following.

a) The ratio of epihalohydrin, which is a reaction product between the terminal hydroxyl group and di-pino-lohydrin, is suitably 1 equivalent or less, preferably 0.01 equivalent, per 1 equivalent of polyether polyol.
~1 equivalent.

Epichlorohydrin is suitable as the epihalohydrin.

b) Alkylated (cationized) or neutralized nitrogen atoms contained in the molecule.

Alkylation is obtained by quaternizing part or all of the nitrogen atoms with an algylating agent. As the alkylating agent, alkyl chlorides such as methyl chloride and long-chain alkyl chloride, and dialkyl sulfates such as dimethyl sulfate and diethyl sulfate can be used.

Further, the neutralized product is obtained by neutralizing the nitrogen atoms in the molecule with an organic acid such as an organic sulfonic acid, a sulfuric acid ester, or a carboxylic acid, or an inorganic acid such as hydrochloric acid or sulfuric acid. As the acid, organic acids are preferred.

The ratio of alkylation and neutralization is suitably 1 equivalent or less, preferably 0.01 to 1 equivalent, per 1 equivalent of polyether polyol.

C) Anionized product of terminal hydroxyl group.

Carboxyne alkylation of part or all of the terminal hydroxyl group
compounds, sulfuric acid esterified compounds, phosphoric acid esterified compounds, and salts of these compounds. The anionization ratio is suitably 1 equivalent or less, preferably 0.01 to 1 equivalent per equivalent of polyether polyol.

d) Carboxylic acid ester with terminal hydroxyl group.

The esterification ratio is 1 equivalent or less, preferably 0.01 to 1 equivalent of a carboxylic acid derivative that reacts with a carboxylic acid or hydroxyl group to form an ester per equivalent of polyether polyol.
1 equivalent.

The OOM additive of the present invention contains the aforementioned polyether polyol or its derivative as an active ingredient, but may optionally contain other ingredients as long as the effects of the present invention are not impaired. Such other ingredients include known OOM additives.

There are alkaline substances, surfactants, etc.

The additive for OOM of the present invention is 0.01 to 0 for OOM.
．． By adding 5% by weight, preferably 0.05 to 0.3% by weight, coal particles can be stably dispersed in fuel oil, and the viscosity of 00M can be kept low.

The OOM additive of the present invention is anthracite and bituminous coal.

It can be easily applied to sub-bituminous coal, lignite, etc., and its average particle size is usually less than 100 microns, especially 74
It is preferable that the particles contain particles of 50 or more microns or less in size.

The coal concentration in 00M using the additive of the present invention is 30-7
A range of 0 weight ratio, preferably 40 to 65 weight ratio is suitable.

Oils that can be used when producing OOM using the additive of the present invention include crude oil, heavy oil, and light commercial oil.

Any hydrocarbon oil such as gasoline may be used, but in consideration of economic efficiency, it is advantageous to use crude oil and heavy oil.

To disperse coal in oil using the additive of the present invention,
For example, the additive may be dissolved in fuel oil and then mixed with pulverized coal, or the additive may be added to a mixture of pulverized coal and fuel oil. The temperature at which the additive of the present invention is mixed with coal or oil is arbitrary, for example, at 50 to 150°C.

The mixing pressure may be normal pressure, but may be reduced to perform 00M0 degassing.

When producing OOM using the additive of the present invention, there is no problem in adding water, but if the amount of water is too large, it will cause a decrease in combustion efficiency, so please be careful when adding water. Addition of water should be avoided. Coal differs depending on the drying method, but it usually has adhering water, so
The amount of moisture allowed in 00M is 10% or less in 00M, including water adhering to the coal and water added from outside.
The weight of a good burial mound should be 5 or less.

When producing OOM consisting of pulverized coal, fuel oil, and additives using the additive of the present invention, the method and order of addition of each of these components, the agitator for mixing, and the stirring conditions are There are no restrictions unless the action is particularly inhibited.

According to the findings of the present inventors, OOM additives adsorb to the surface of pulverized coal to form a hydrophobic adsorption layer, and this adsorption layer is thick and does not dissolve in oil, which contributes to the dispersion of COM. It was discovered that there are important things to do to increase stability. Furthermore, because this adsorption layer strongly adsorbs to the surface of coal particles,
It is desirable that the molecules of the additive have a structure that facilitates the formation of a two-layer structure consisting of a hydrophilic portion and a hydrophobic portion. It is important that a COM additive that satisfies these properties consists of a relatively small hydrophilic group and a hydrophobic group composed of a large number of branched chains, and that the hydrophobic group is located at the end of the molecule. Hydrophobic branched chains tend to form a planar adsorption layer on the surface of coal particles when additives are adsorbed to the coal particles, so #1, which has many branched chains, has good dispersion stability and low viscosity. OOM can be manufactured. The present invention was made based on such knowledge, and the additive of the present invention uses a polyamine having a large number of active hydrogens or a modified product thereof as a hydrophilic group portion, and an alkylene oxide having 3 or more carbon atoms as the active hydrogen. The hydrophobic group is an oxyalkylene/structure consisting of a branched chain corresponding to the number of active hydrogens obtained by adding , and the molecular terminal is a parent 1 which is very small in proportion to the size of the branch.
The hydroxyl group is also I-〈is X(;.

Since it is an oil base, it can be virtually ignored, and as a result, OOM produced using it can be imparted with excellent dispersion stability and low viscosity.

Next, the present invention will be explained in more detail with reference to Examples. Note that "parts" and r % and 1 (d) shown in the examples are all based on weight. Also, the properties of the Middle East heavy oil and Pelmont coal used in the examples are shown below.

Middle East heavy oil: Calorific value 10310kcat/kp+JIs K 226
51, specific gravity 0.957/).

Pour point -2.5℃ (J Engineering SK, 22691, flash point 94.0℃fJ'I8K 22651, ash content 02
%fJISK 2272+, Moisture 0 old staff + J engineering s K
22751, elemental analysis value (Yanagimoto organic automatic elemental analyzer fR) O: 84.17, H: 13.06%, S
: 2.39%, N: 0.25.

0:0.13%, O4:3.3%, V:65pp
m, Na: 15 ppm0 Belmont coal (produced in Australia): calorific value 6550 kd (JIS M 8814), ash content 15.95 + JIS M 81H21, moisture 3.2
5 qb (J engineering Sλ488111, fixed carbon 49.3
5% (JIS M 88121, elemental analysis value (JIS
M88131 C: 16.17 section, H: 4゜71 regret,
N: 1.23, O: 8.44%, S: 0.30
%, Ot: 0.03%, Na: 0.04%.

Example Various additives were added to Middle East heavy oil and immersed in an oil bath at 70°C. Belmont charcoal, which had been crushed to pass 80 through a 200 mesh (74μ mesh) sieve, was added to the above Middle East heavy oil, heated for 1 hour, and after the temperature became constant, a lab mixer (manufactured by Tokushu Kikako) was added. ) at 5000 rpm
A sample pulverized coal-oil mixed fuel was prepared by stirring for a minute.

Middle East heavy oil is 0.03%, Belmont coal is 3.25%
Since each sample contains water, the water content was subtracted from each sample before it was weighed. The additive was used in external cutting with the total amount of coal 1 heavy oil and water contained therein as 100%.

The fluidity and stability of the prepared samples were determined by the following method.

The test device used was a stainless steel cylinder with an inner diameter of 5.3 cm and a height of 24 cm, and a fluid outlet with a stopper located 6 cm from the bottom. Put the sample into this cylinder to a height of 18L:rn from the bottom, and
It was left standing in a constant temperature bath at 0°C for one month. After 1 month, diameter 5
A glass rod weighing 202 mm 1 was dropped from the top of the cylinder, the time it took to reach the bottom (hereinafter referred to as rod penetration time) was measured, and then the cylinder was removed with a stopper.
], the sample above this position was removed, and the remaining sample was taken out and the concentration in the lower layer of the coal was determined. The coal content was dissolved, the coal content was separated by filtration, and the coal content was weighed and expressed as weight t%.The types of additives used are shown in Table 1 (
The coal concentration, the amount of additive used, the viscosity of the sample, the rod penetration time, and the lower layer concentration of coal are summarized in Table 3.

Claims (1)

[Claims] 1. Polyether polyols with a molecular weight of 100,000 to 2,000,000 or derivatives thereof obtained by adding alkylene oxide having 3 or more carbon atoms to polyamines with a molecular weight of 10,000 to 200,000 or modified products thereof are effective. Additive for coal-oil mixed fuel as a component. 2. The additive according to claim 1, wherein the molecular weight of the polyamine or its modified product is less than 50 times the molecular weight of the polyether polyol or its derivative. 3. The additive according to claim 1, wherein the polyamine is polyethyleneimine or a derivative thereof. 4. The additive O according to claim 1, wherein the polyether polyol derivative is a reaction product of polyether polyol and ebihalohydrin. 5. 2. The additive according to claim 1, which is a compound partially or entirely cationized or neutralized with an organic or inorganic acid. 6. Claim 1, wherein the polyether polyol derivative is a compound obtained by anionizing some or all of the terminal hydroxyl groups of the polyether polyol by carboxyalkylation, sulfuric acid esterification, or phosphoric acid esterification, or a salt thereof. additives. 7. The additive according to claim 1-2, wherein the polyether polyol derivative is a compound obtained by converting some or all of the terminal hydroxyl groups of the polyether polyol into a carboxylic acid ester, and the parent compound is a salt thereof.