JPS6014075B2 - Additive for pulverized coal-oil mixture - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an additive for pulverized coal-oil mixtures for producing pulverized coal-oil mixtures with 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. A mixture of pulverized coal and pond does not have the above-mentioned drawbacks, and the price per calorific value is lower than that of oil alone, so it has a high practical value. However, simply mixing pulverized coal and oil does not yield a satisfactory pulverized coal-oil mixture because the pulverized coal particles settle and separate due to the difference in specific gravity, coagulate, and lose fluidity. Therefore, it is important to find and develop additives that improve stability and fluidity, and the inventors have already succeeded in overcoming the above problems and finding and developing effective additives. This made it possible to put into practical use a powdered coal-oil mixture.

(Japanese Unexamined Patent Publication No. 53-78207) The present inventors have developed a powdered coal that maintains stability and fluidity for a longer period of time and is more economical.
As a result of intensive research in order to obtain a unique product, we discovered and succeeded in producing an additive for powdered coal-oil mixtures, which will be described later, and succeeded in producing an extremely superior powdered coal-oil mixture.

According to the present invention, a powdered coal-oil mixture with significantly improved stability and fluidity than conventional ones can be obtained, and even when stored for a long period of time at not only room temperature but also high temperature, sedimentation of powdered coal hardly occurs, and even if it does occur slightly. However, due to the excellent action of this drug, there is almost no agglomeration of the settled pulverized coal, so it can be re-fluidized with just a simple tsukihai. of course,
If it is for a short period of time (about 15 days), there is no need to worship the fly. This has made it possible to safely transport the pulverized coal-oil mixture over long periods in tankers, store it in tanks, and transport it through pipelines and pipes. In addition, the amount of this drug required to be used was smaller than that of the conventional method, which further promoted the commercialization of the pulverized coal and oil mixture from an economical point of view. The coal used in the pulverized coal mixture includes various types of coal, such as anthracite, blue coal, sub-moat blue coal, lignite, etc., regardless of type or production area, and regardless of chemical composition or moisture content.
Anything can be used.

The coal is either left as it is, or coarsely crushed and placed in oil, and made into pulverized coal directly in oil using various wet crushers;
Alternatively, it may be made into pulverized coal using a normal dry pulverizer.

However, a wet pulverizer is better because it improves the stability of the pulverized coal-oil mixture and prevents spontaneous combustion and dust during pulverization. Moisture in the coal may be removed during dry pulverization, or during or after wet pulverization, and if the coal contains a small amount of moisture, there is no problem even if it is not removed. The particle size of pulverized coal is judged from combustibility, and is usually an average particle size of 200.
It is preferable to have a particle size of less than 100 mm, and even smaller particle size of 100 mm or less is preferable, but as far as the physical properties such as the stability of the pulverized coal-oil mixture are concerned, even larger particles are acceptable. The content of this pulverized coal is 20 to 7% by weight based on the final mixture, and if the pulverized coal is contained in an amount of 7% or more by weight, the viscosity becomes extremely high and fluidity is lost, which is undesirable. If it is less than 1% by weight, it is not preferable because the economic advantage associated with the inclusion of pulverized coal decreases. Therefore, 20
Although it can be contained in a range of 7 to 7% by weight, a range of 30 to 6% by weight is more preferred. In addition, the oil used in the pulverized coal-oil mixture includes petroleum crude oil, various types of oil obtained from crude oil, such as kerosene, light oil, A
Oils and waste oils commonly used as fuel such as heavy oil, B heavy oil, C heavy oil, etc., ethylene cracked residual oil, creosote oil, anthracene oil, various blended oils, etc., such as gas station waste oil (automobile lubricating oil, cleaning oil), iron works 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.

Even if a pulverized coal-oil mixture is made using only a single oil or a pre-blended oil, it is not necessary to make a pulverized coal-oil mixture using a single oil (preferably petroleum crude oil or heavy oil) and then mix other oils. You can also buy food. Water may be mixed into the coal-oil mixture, or may be added by the manufacturer or user, but transportation costs, storage costs, and other general and administrative costs will be incurred based on the volume of water. This is undesirable because it increases the heat of vaporization during combustion and increases heat loss, so the smaller the amount, the better.

On the other hand, water is allowed to be mixed in a small amount because it has the property of improving the stability of the pulverized coal-oil mixture and has the effect of reducing the amount of NO and byzine in the exhaust gas during combustion.

Therefore, the total water content is preferably 9% by weight or less, preferably 6% by weight or less, and may not be contained at all. However, when about 0.5% to 3% of water is added later together with the drug, stability is often significantly improved. The additive for pulverized coal-oil mixtures according to the present invention is [a] di- or mono- or di-containing an alkyl group having 6 to 10 carbon atoms in the molecule.
With monomixed alkyl sulfosuccinate ester salt [
W Characterized by containing a polyether having a molecular weight of 1,000 to 100,000 by adding alkylene oxide to an organic compound having one or more phenolic OH groups and two or more total active hydrogens as a starting material. It is something to do.

Specific examples of the alkyl sulfosuccinate ester salt described in {a' above include the following.

Sodium dihexyl sulfosuccinate, mono-sodium hexyl sulfosuccinate, di-mono mixed sodium hexyl sulfosuccinate, di-n-octyl sodium sulfosuccinate, mono-sodium n-octyl sulfosuccinate, mono-di-mixed sodium hexyl sulfosuccinate , Sodium di-2-ethylhexylsulfosuccinate, Sodium mono-2-ethylhexylsulfosuccinate, Sodium mono-2-ethylhexylsulfosuccinate, Sodium di-n-decylsulfosuccinate, Sodium mono-n-decylsulfosuccinate, Sodium mono-2-ethylhexylsulfosuccinate Mixed-n-decyl sodium sulfosuccinate, di- or mono- or mono-di mixed sodium alkyl sulfosuccinate obtained from alcohols with a distribution of carbon numbers of 6 to 10. In addition, monovalent metal salts such as ammonium salts and potassium salts corresponding to these are also effective, but di- or di-mono mixed salts are preferred, particularly di- or mono-di-merized sodium 2-ethylhexylsulfosuccinate. Salt is preferred. Specific examples of the polyether compounds described in {b} above will be described below.

The polyether mentioned here is the general formula Z [(RO)nH]m where Z is the residue of the above starting material.

R is a residue of alkylene oxide such as ethylene, propylene, butylene, ethylene chlorohydrin, ethylene carbonate, or tetrahydrofuran, and n is a number determined by the degree of polymerization of the alkylene oxide. m is the number of active hydrogens including the phenolic OH group that Z has, and is at least 2 or more, preferably 3 or more. RO may be a single substance or two types may be used, and the RO may be of a block copolymerization type or a random copolymerization type while the arrangement order remains the same. However, if the surfactant is a copolymer type, it is generally a block copolymer type, and preferably,
Ethylene oxide is added to make the terminal a hydrophilic group. Examples of starting materials corresponding to Z include: 01 Polyhydric phenols e.g. catechol, resorcinol, hydroquinone, pyrogallol'2} Polyhydric naphthols e.g. naphtoresorcinol, Q-naphthohydroquinone, etc. dioxynaphthalene, trioxynaphthalene {31 Phenolic is active in addition to groups Substituted phenols containing one or more hydrogen atoms, preferably two or more hydrogen atoms, such as aminophenol, oxybenzoic acid, gallic acid (4-phenol, resorcinol, naphthol, or substituted phenols such as metacresol, metaxylenol, metaethyl Phenol, orthocresol, /acresol, 2.6
In a condensate formed by condensing xylenol etc. with an aldehyde such as formaldehyde, acetaldehyde, benzaldehyde or a ketone such as acetone under an acidic or basic catalyst, at least two or more phenolic O
Condensate having an H group 5) Substituted phenols containing one or more, preferably two or more active hydrogens in addition to the phenolic OH group, such as aminophenol, oxybenzoic acid, gallic acid, etc., and aldehydes, such as formaldehyde,
acetaldehyde, benzaldehyde or ketones,
For example, a condensate having at least two or more phenolic OH groups in a condensate condensed with acetone under an acidic or basic catalyst.Here, the phenolic PH group refers to phenol, naphthol, substituted phenol, substituted naphthol. , polyvalent phenol, polyvalent naphthol, etc. means an OH group directly bonded to an aromatic ring.

The present inventors have already found that the drug described in 'b} above alone exhibits an excellent effect, and has filed a patent application. However, when these drugs are used in combination with the drug described in 'a--', We found that it had even better effects and released it.

Furthermore, the additive of the present invention can be used by dissolving it in a solvent, particularly a lower alcohol such as methanol, ethanol, isopro/gnol, n-pro/gnol, isobutanol, n-butanol, ethyl cellosolve, or a mixture of lower alcohol and water. Although the effect is better when the solvent is used, it can also be used without using a solvent. Furthermore, there is no hindrance to the combined use of other surfactants in appropriate amounts.

As is clear from the comparison in the examples below, mono- or di-alkyl sulfosuccinate ester salts alone,
It is not preferable because the stability of the pulverized coal and oil mixture is impaired, and it is essential to use the ingredients described in 'a} and the ingredients described in {b} in combination, and the combined ratio is [a'/'b} = 95/5 ~ 5/95
Preferably 90/10 to 60/40 or 10/90 to
It is 40/60.

In order to stabilize and fluidize a pulverized coal-oil mixture using the additive of the present invention, the additive may be added after dry-pulverized pulverized coal is mixed into oil, or the additive may be dissolved in oil in advance. It is sufficient to add dry-pulverized pulverized coal or to mix all three at once, and it is also possible to add water to each of them.Also, additives can be added later to the wet-pulverized pulverized coal-oil mixture, or they can be added to the oil. It may be added after addition, and in this case also 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 0.08% by weight in the mixed fuel.
~0. The upper limits of 5% and 0.8% by weight are simply values for economic reasons.

According to the present invention, when forming a dispersion system consisting of additives, pulverized coal, oil, and water if necessary, any temperature can be adopted, for example, mixing at 50 to 120 qo, and the mixing pressure can be elevated pressure, normal pressure, or reduced pressure. It may be used during degassing, and there are no restrictions on the strainer and the conditions as long as the effect of the additive is not inhibited, but a strong rope with a circumferential speed of 2/sec or more is particularly preferred.

Next, the present invention will be explained in more detail with reference to Examples. Note that all parts and percentages shown in Examples are based on weight. Moreover, the birch penetration test shown in the following examples was conducted as follows. The test equipment was a stainless steel cylinder with an inner diameter of 5.5 and a height of 20.
Use a cathedral that has an outlet with a stopper on each layer.

Fill this cylinder with a specified amount of mixed fuel from the bottom to a height of 1.5 cm, cover the top of the cylinder with a lid with a guide hole in the center, and insert a glass rod with a smooth tip with a diameter of 5 ribs through the center guide hole. (Total weight: 20 mm) was dropped vertically, and the time from when the tip penetrated into the mixed fuel until it reached the bottom of the cylinder was measured, and this time was defined as the rod penetration time. The shorter this time, the less sedimentation and pressure decomposition of pulverized coal occurs, resulting in a mixed fuel with excellent fluidity. After the test, remove the stopcock at a height of 12 arcs from the bottom and take out the mixed fuel above (i.e., the mixed fuel in the cylinder at a height of 12 to 18 arcs from the bottom) and use it as the upper layer sample. , its viscosity and coal concentration were measured. Next, the stopcock at the 6th depth point from the bottom was removed, and the mixed fuel above that point was taken, and its viscosity and coal concentration were measured as a middle layer sample.Finally, the stopper at the bottom was removed, and the remaining mixed fuel was taken. The viscosity and coal concentration of the lower layer sample were measured. The rod penetration test and viscosity measurement described above were both carried out at 7000.
After adding it to the container, it was heated by hand for about 2 minutes at 70o0, and then stirred for 10 minutes using a homomixer at a circumferential speed of 3 m/sec and 70qo to obtain a mixed fuel.

After conducting a static pupil test on this product at 70qo for 30 days,
The award-winning test and the viscosity and 0 coal concentration of the upper, middle, and lower layers were measured.

The results obtained are shown in Table 1. From Table 1, this mixed fuel is 70 qo, the penetration time after the 30-day static calendar test is about the same as that immediately after production, and there is little change in viscosity or coal concentration before and after the test, so it can be transported by large tanker or tanked. It can be seen that it can withstand long-term storage. Reference Example A mixed fuel was obtained under the same conditions as in Example except that the dispersant was changed.

The properties of this product before the test and the results after the 30-day static test at 70 qo are shown in Table 2. Table 2 shows that these mixed fuels cannot withstand transportation in large tankers or long-term storage in tanks because the coal separates and is compressed. & Kashi carp boat ship

Rito ○ A Table 2 (reference example)

Claims (1)

[Claims] 1 (a) a di- or mono- or di-mono mixed alkyl sulfosuccinate salt having an alkyl group having 6 to 10 carbon atoms in the molecule, and (b) a phenolic OH group containing 1
and adding an alkylene oxide to an organic compound having two or more total active hydrogens as a starting material,
An additive for a pulverized coal-oil mixture, characterized by containing a polyether having a molecular weight of 1,000 to 100,000.