JPS6014078B2 - Additive for pulverized coal-oil mixture - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an additive for a powdered coal-oil mixture for producing a powdered coal-oil mixture 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. There was a problem with fuel. A mixture of pulverized coal and oil does not have the above-mentioned drawbacks and has high practical value because it has a lower price per calorific value than oil alone. However, simply mixing pulverized coal and oil does not result in 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.

(Tokukan Sho 53-78207) The present inventors have continued their intensive research in order to obtain a more economical pulverized coal-oil mixture that maintains stability and fluidity for a longer period of time, and as a result of the following. We discovered and succeeded in developing an additive for finely powdered coal-oil mixtures, and succeeded in producing an extremely excellent finely divided coal-oil mixture.

According to the present invention, it is possible to obtain a pulverized coal-oil mixture with significantly improved stability and fluidity compared to conventional ones, and even when stored for a long period of time at high temperatures as well as at room temperature, the pulverized coal hardly settles, even slightly. Even if this occurs, due to the excellent action of this drug, there is almost no agglomeration of the settled pulverized coal, so
It can be re-liquidized with just a simple ritual. Of course, if it is for a short period of time (about 15 days), there is no need to use a lily pad. This has made it possible to safely transport the pulverized coal-oil mixture in tankers over long periods of time, or to transport it through pipelines and piping. In addition, the amount of this drug required to be used was smaller than that of the conventional method, which further promoted the practical application of pulverized coal general mixtures from an economic standpoint. The coal used in the pulverized coal mixture includes any type of coal, such as anthracite, charcoal, subbituminous coal, lignite, etc., regardless of its type or production area, or regardless of its chemical composition or moisture content. Also available.

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, the wet pulverization method is better because it improves the stability of the pulverized coal-oil mixture and prevents spontaneous combustion and dust during pulverization. Moisture in coal may be removed during dry pulverization, during green pulverization, or after pulverization; if the coal contains a small amount of moisture, there is no problem even if it is not removed. Judging from the fuel property, the particle size of the fine coal is usually preferably 200 mm or less, and even smaller particle size of 100 mm or less is preferred, but as far as physical properties such as stability of the fine coal-oil mixture are concerned, the particle size may be even smaller. There is no problem even if the size is large. The content of this pulverized coal is 20 to 7% by weight based on the final mixture. If the pulverized coal is contained in an amount of 7% or more by weight or more, the viscosity becomes extremely high and fluidity is lost, which is not preferable. If the amount is less than 2% by weight, it is also undesirable because the economic advantages associated with the inclusion of pulverized coal are reduced.

Therefore, it can contain 20 to 7% by weight, but 30 to 6% by weight.
Even more preferred is a weight percent of . In addition, the oils used in the pulverized coal and oil mixture include petroleum crude oil, various types of oil obtained from crude oil, such as kerosene, light oil, A heavy oil, B heavy oil, C heavy oil, etc., ethylene decomposition residual oil, creosote oil, anthracene oil, etc. , oils and waste oils commonly used as fuel, such as various blended oils, such as gas station waste oil (automobile lubricating oil, cleaning oil), ironworks waste oil (machine oil, cutting oil, cleaning oil, and mixtures thereof), oil tankers, etc. This refers to waste oil from ships, waste oil from general chemical factories, etc., and also includes mixtures of both. Among them, it is preferable to use petroleum crude oil, B heavy oil, and C heavy oil.

Even if you make a pulverized coal-oil mixture using only a single oil or a pre-blended oil, you can 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 grill it in a moat. 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 evaporation during combustion and increases heat loss, so the smaller the amount, the better.

On the other hand, since water 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, a small amount of water is allowed.

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, if approximately 0.5 to 3% water is added together with the drug,
Stability is often significantly improved. The additive for powdered coal-oil mixture according to the present invention is {a-6 carbon atoms in the molecule.
with di- or mono- or di-mono mixed alkyl sulfosuccinate ester salts having ~10 alkyl groups {b
- Molecular weight 1000-1 using an aromatic compound as a starting material
It is characterized by containing a compound obtained by condensing 00,000 polyether compounds using formalin.

Specific examples of the alkyl sulfosuccinate ester salts 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-di-mixed-2-ethylhexylsulfosuccinate, Sodium di-n-decylsulfosuccinate, Sodium mono-n-decylsulfosuccinate, Sodium mono-n-decylsulfosuccinate Dimixed-n-decyl sodium sulfosuccinate, di- or mono- or mono-di-mixed sodium alkyl sulfosuccinate obtained from alcohols having a distribution of carbon atoms of 6 to 10. Monovalent metal salts corresponding to these, such as ammonium salts and potassium salts, are also effective, but di- or mono-di mixed-2-ethylhexylsulfosuccinic acid sodium salt is particularly preferred. Hereinafter, specific examples of the formalin condensate of the polyether compound described in 'b-' above will be explained.

Molecular weight 100 using the aromatic compound mentioned here as a starting material
0 to 100,000, preferably 2,000 to 20,000 polyether compounds (hereinafter referred to as polyethers) mean a compound having an aromatic group and one or more active hydrogen groups as a starting material, and an alkylene oxide such as ethylene oxide or propylene. It is made by addition polymerizing oxide or butylene oxide and at least one of ethylene chlorohydrin, ethylene carbonate, and tetrahydrofuran to a predetermined molecular weight.

In this case, if there are two or more types of alkylene oxide,
There is no problem even if the copolymerization type is random or block copolymerization. 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. As a compound having an aromatic group and an active hydrogen, the following may be used arbitrarily: ・Tecol, resorcinol, hydroquinone, pyrogallol, nonylphenol, octylphenol, dodecylphenols Alkylene oxide adducts of alkyl-substituted phenols such as bisphenol A, pisphenol S, etc. Alkylene oxide adducts of naphthols such as dioxynaphthalene such as naphresorcin, Q-naphthohydroquinone, etc. In general, it is known that phenol resins and xylene resins have methylene bridges between aromatic rings when reacted with formalin under acidic conditions.

Therefore, in order to condense a polyether compound using formalin as in the present invention, the above-mentioned known techniques can be used, but it is generally carried out as follows.

That is, 0.1 to 10 equivalents of formalin, preferably 0.5 to 5 equivalents, and 0.05 to 0.005 equivalents of acidic catalyst are added to 1 equivalent of polyether compound to give 60 to 100 equivalents of formalin.
The temperature was raised to
The reaction was completed by raising the temperature to 80 qo.

The present inventors have already found that the drug described in {b' above alone exhibits an excellent effect, and has filed a patent application, but when these drugs are used in combination with the drug described in 'a', We have discovered and demonstrated that it has even better effects. The additive of the present invention can also be used as a solvent, especially methanol, ethanol, isopropanol, n-propanol, isoptanol,
Although the effect is better when used by dissolving it in a lower alcohol such as n-butanol or ethyl cellosolve, or a mixture of a lower alcohol and water, 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-oil mixture is impaired, and it is essential to use the ingredients described in 'a} and the ingredients described in {b' together, and the combined ratio is 'a} no' b) = 95/5 ~ 5/9, preferably 90/10 to 60/40 or 10 to 90
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 a mixture of wet-pulverized pulverized charcoal and oil, or they can be mixed with 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. % by weight of the neck, and 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 is adopted, for example, mixing is performed at 50 to 120°C, and the mixing pressure is pressurized,
It may be degassed at normal pressure or reduced pressure, and the rope slinging machine and rope slinging conditions are not restricted as long as the action of the additive is not inhibited.
In particular, a strong frame with a circumferential speed of 2 M'sec or more is preferable.

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. Further, the comb penetration test shown in the following examples was conducted as follows. As a test device, Naiyo 5.5 skin height 2
A stainless steel cylinder with a diameter of 0.6 mm from the bottom,
Use one that has an outlet with a stopper at each layer of the 12 arcs.

Fill this cylinder with the specified mixed fuel to a height of 18 mm from the bottom, cover the top of the cylinder with a lid with a guide hole in the center, and insert a smooth glass rod with a diameter of 5 mm at the end through the center guide hole. (Total dead 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 compaction of pulverized coal, resulting in a mixed fuel with excellent fluidity. After the test, remove the stopper at the 12th position from the bottom, take out the mixed fuel above it (that is, the mixed fuel in the cylinder at a height of 12 to 18 feet from the bottom), and then sample the upper layer. The viscosity and coal concentration were measured.

Next, the stopcock at a position 6 arcs from the bottom was removed, 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 detected, and its viscosity and coal concentration were measured as a sample of the lower layer. Both the rod penetration test and the viscosity measurement described above were conducted at 70 qo. Example The prescribed amounts of coal, petroleum, additives and water shown in Table 1 were added to 1
In addition to the final container, after holding a hand lantern for about 2 minutes at 7-bi-0,
Using a homo mixer, the mixture was mixed for 10 minutes at a circumferential speed of 3 W/sec and 7000 to obtain a mixed fuel.

This product was subjected to a static test at 70° C. for 30 days, and then subjected to a penetrating test and the viscosity and 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 has a birch penetration time of 7Bi○ after the 30-day static taka test, which 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 is transported by large tanker. It also shows that it can withstand long-term storage in tanks. Reference Example A mixed fuel was obtained under the same conditions as in the example except that the example and the dispersion example were changed.

The properties of this product before the test and the results after the 30-day static counterfeit 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 densifies. ＆Run rudder vessel L Nza Shimosu) ト日○ 口二'' Nza Shimoiri).

〕to ○ ○ Table 2 (reference example)

Claims (1)

[Claims] 1 (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) polyether with a molecular weight of 1,000 to 100,000 using an aromatic compound as a starting material. An additive for a pulverized coal-oil mixture, comprising a compound obtained by condensing a compound with formalin.