JPS6023799B2 - Mixture of pulverized coal and hydrocarbon oil - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a mixture of powdered coal and hydrocarbon oil or emulsified hydrocarbon oil (hereinafter referred to as mixed coal oil), which has excellent stability and does not precipitate or solidify over a long period of time.

More specifically, the present invention relates to an inexpensive stabilizer that enables the production of highly stable carburized oil that does not precipitate and solidify over a long period of time.

Conventionally, coal is a solid, making it difficult to transport and control during combustion, making it inferior to petroleum, which is a liquid, as an energy source.

In order to overcome these problems, in Japan, prior to World War II, research was being actively conducted at the Naval Fuel Center and other institutions to create pork fuel, which was made by turning coal into pulverized coal and mixing this with petroleum. However, simply mixing pulverized coal with a normal particle size distribution and petroleum causes the coal particles to settle and separate due to the difference in specific gravity, creating a hard layer with no fluidity. Methods have been considered to extremely slow down the sedimentation rate by reducing the total amount of coal particles to less than 10 French in diameter, but both methods are expensive and undesirable in practice. On the other hand, in order to prevent sedimentation of pulverized coal, many methods have been studied to produce stable mixed coal oil by adding stabilizers such as polymeric substances or emulsifiers, or water to petroleum and coal.

For example, typical old pottery products include protective materials such as waist, gelatin, gum arabic, and starch; in addition, paraffin, sericin, lanolin, petrolatum, and similar materials include wax, tallow, and wool. Examples include fat. However, although all of these stabilizers have some stabilizing power, they are not decisively effective. Later, metallic fatty acid soaps were considered, and the metallic ones include AI, Mn, Co, Zn, Ca, Na, K, Pb,
Mg, etc., and soaps such as oleic acid, stearic acid, and palmitic acid were used as fatty acids.

In addition, there are methods for adding alkali to form salts with humic acids in coal to prevent sedimentation of coal particles, and for dispersing coal particles using coal-based distillate oils such as anthraceso, naphthalene, phenanthrene, etc. Numerous research examples have been reported in the past, including methods for producing stable mixed coal oil by adding appropriate amounts of tar oil, anthracene oil, creosote oil, etc. containing phenol and other components. However, it has excellent flammability,
In addition, there is no stabilizer that is effective in small amounts, and in most cases, the amount used is at least several percent of the mixed coal oil, and in many cases it is 10% or more of the mixed coal oil.
% or more is required, resulting in high cost and an economical problem.

Furthermore, metal soaps contain a large amount of metals that are harmful to the human body, so there is a risk of pollution problems.

In addition, adding an appropriate amount of coal-based heavy oil is an effective means of producing stable peat oil, but the amount used is only 1% of that of carburized oil.
If we consider its use as an energy source, it would be necessary to expand the tar industry, which is already in short supply at present, and furthermore, tar vapor is harmful and dangerous, so it is difficult to handle it. Considering that sufficient care must be taken when using mixed coal oil, this poses a major problem in terms of the supply of mixed coal oil and pollution.

In view of the above circumstances, the present inventors have decided to stabilize mixed coal oil, which is free from the risk of pollution, is inexpensive, is effective as a stabilizer, and can be supplied to some extent domestically if it is used in large quantities in the future. As a result of considering the agent, 20,000
or more and has an aromatic hydrocarbon content of 5% by weight
The inventors have found that the object can be achieved by using the oxidized hydrocarbon oil containing the above as a stabilizer, and have completed the present invention.

In order to carry out liquid phase oxidation of the hydrocarbon crab fraction, which is the raw material for the oxidized oil used as the stabilizer of the present invention, at about 100 to 2000 C, it is necessary to have a hydrocarbon fraction with a boiling point of less than 200 qC. Also, those with an aromatic hydrocarbon fraction of less than 5% by weight have less aromatic ring compounds and are less compatible with coal. 5% or more by weight is used.

When the oxidized oil obtained by liquid phase oxidation was analyzed in detail using an infrared absorption spectrum, it was found that it exhibited strong absorption in the vicinity of 1630 to 1750 skin-1.

This absorption is due to carbonyl groups found in compounds such as organic acids, ketones, aldehydes, acid amides, and acid imides. Furthermore, when we measured the acid value by neutralizing the oxidized oil with an alkaline solution such as caustic soda or potassium solution, we found that there was an extremely strong correlation between the intensity of the infrared absorption spectrum and the acid value. The main component of the carbonyl group can be determined to be carboxylic acid. Table 4 shows the relationship between the reaction conditions of liquid phase oxidation and the amount of carboxylic acid produced.

From Table 4, among the extract oils produced from the solvent refining equipment for lubricating oil fractions, 15 Ship S (Bright Stock) extract oil and #10 extract oil are used as raw materials and copper naphthenate is used as a catalyst. 60% oxygen, 40% nitrogen
It can be seen that when liquid phase oxidation is carried out using a mixed gas of 150 qC, a minimum reaction time of about 4 hours is required.

The exact mechanism by which carboxyl groups in oxidized oil contribute to the stabilization of mixed coal oil is not clear, but it is thought to be as follows.

When comparing coal and petroleum, coal has a highly aromatic structure and high oxygen content, whereas petroleum is mainly composed of hydrocarbons and has low aromaticity. For this reason, coal and petroleum are not compatible, and if pulverized coal and petroleum are simply mixed, the pulverized coal particles tend to settle. Therefore, aromatic hydrocarbon fraction according to the present invention Table 4 Reaction conditions of liquid phase oxidation and production amount of carboxylic acid Altering agent: Oxygen 60% Nitrogen 40% Catalyst:
When an oxidized oil containing at least 0.1 milligram equivalent per gram of carboxyl groups obtained by oxidizing a hydrocarbon fraction containing at least 5% by weight of meta (copper naphtheoate) units is used as a stabilizer, aromatic Not only do group hydrocarbons blend well with coal, but also the carboxyl groups are adsorbed to the surface of the pulverized coal particles due to van der Waals forces, mainly consisting of magnetism, i.e., hydrogen bonding force, acting on the coal. It is presumed that this would exhibit a synergistic effect and make it possible to obtain an even more stable mixed coal oil.

Hydrocarbon oils used in the present invention include coal-based fuel oils that are liquid at room temperature, such as crude oil, crude oil (crude oil from which the Ganlin fraction has been removed), atmospheric residual oil, kerosene, light oil, A heavy oil, B heavy oil, C Examples include liquids obtained from heavy oil, coal-based liquefied oil, oil sands, oil shale, etc.

The fine coal used in the present invention is fine coal having an average particle diameter of about 20 to 80 particles, which passes 80% or more of the 100-mesh ring of a tyler, which is usually used in large boilers. Next, as an embodiment of the present invention, in an oil refinery or the like, the oxidized oil obtained by liquid-phase oxidation of the ZJ extract and the aromatic hydrocarbon fraction by-produced from the solvent refining equipment for lubricating oil is used to stabilize mixed coal oil. When used as an agent, a blended coal oil with excellent stability was obtained.

The lubricating oil fraction used in the present invention is obtained by distilling heavy oil obtained as a distillation residue by atmospheric distillation of crude oil under reduced pressure, has a boiling point of 300 to 600 °C in terms of atmospheric pressure, and is an aromatic hydrocarbon. This refers to a fraction containing 5% by weight or more of crab. A large number of solvent refining equipment for lubricating oil fractions, such as furfural refining equipment, are currently in operation in Japan, and the extract produced as a by-product from these equipment is an aromatic hydrocarbon fraction of 70 to 70%.
It is easy to oxidize in liquid phase and is oxidized in liquid phase by air or the like at a reaction temperature of about 0 to 200 qo to produce oxygen-containing compounds such as organic acids.

This oxidized extract was added to 0.0% of the charcoal oil.
5-5. If it is added as a stabilizer in an amount of about %, a very stable mixed coal oil can be produced at low cost. The reason why the oxidized oil of this extract is effective as a stabilizer for mixed coal oil is not clear, but firstly, the molecular structure of the extract itself contains many aromatic ring hydrocarbon compounds, similar to coal-based heavy oil. It is thought that it is easy to adapt to the surface of coal, and that oxygen atoms are introduced by liquid-phase oxidation of the extract, so that it has a stronger dissolving property on coal.

Furthermore, the extract produced as a by-product from this lubricating oil solvent refining equipment is produced in Japan at a rate of several tens of cubic centimeters per year, and it contains less harmful metals than the metal soap mentioned above. is extremely small, and there is almost no adverse effect on the combustion furnace or increase in harmful components in the exhaust gas when burning mixed coal oil.

Next, it is already known that it is effective to use emulsified hydrocarbon oil as a measure to reduce nitrogen oxides. By adding about 0.5 to 5.0% by weight to the total weight of 100% of the total weight of 0.5% to 5.0% by weight, it is possible to produce a blended coal oil with very good stability. As the emulsified hydrocarbon oil, the various hydrocarbon oils used in the invention described above are mixed in advance with water in an amount of 2 to 10 parts by volume of water per 10 parts by volume of the hydrocarbon oil. If the mixing ratio of water is less than the above, the stability of the mixed coal oil will deteriorate somewhat, and the nitrogen oxide reduction effect will decrease.
If the amount is more than the above, it becomes difficult to produce a uniform mixed coal oil. Furthermore, when an emulsified hydrocarbon oil is produced by mixing water with a hydrocarbon oil, an emulsified hydrocarbon oil that is more stable can be obtained by using an emulsifier. Emulsifiers include synthetic and natural surfactants, and may also include antifreeze agents, rust preventives, fungicides, and the like. On the other hand, as a stabilizer for mixed coal oil, an oxidized hydrocarbon oil having a boiling point of 200° C. or more and containing an aromatic hydrocarbon fraction of 5% by weight or more, that is, for example, a lubricating oil, is used as a stabilizer for mixed coal oil. Oxidized oil is used, which is obtained by liquid-phase oxidation of extract produced from an oil fraction solvent purification device. Next, examples of the present invention will be shown using a mixed carbon oil source having the properties shown in Table 1, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Table 1 Examples of properties of mixed coal oil sources 1 100 grains of lignite powder that passed 86.3% of Tyler's 200 mesh knots, and 100 grains of oil from which the petroleum fraction of Iranian Hebe crude oil was removed by distillation. ' and oxidation obtained by liquid-phase oxidation of 15 Ship S (Bright Stock) extract oil produced from a lubricating oil solvent refining equipment (furfural method) at an oil refinery at a reaction temperature of 150 pm for 4 hours. 15 S (bright stock) extract oil 3' was placed in a 300 cc beaker, and mixed by coagulation for about 3 minutes using a strainer equipped with a screw-type rotor to obtain mixed coal oil A.

On the other hand, for comparison, oxidized 15-S (bright stock) extract oil 3 obtained by liquid phase oxidation at a reaction temperature of 150 qo for 1 hour was mixed with a rope in the same manner as described above to obtain peat oil A'.
I got it. Furthermore, 100 grams of the pulverized coal and 100 grams of the pulverized oil were combined in the same manner as described above to obtain sieved coal oil B without the addition of a stabilizer. Table 2 shows the state of the obtained mixed coal oil after 3 weeks of standing. Example 2 Tyler's 200 mesh fibers were used as fibers. 3% anthracite powdered coal, 100M oil from which the Ganlin fraction of Iranian heavy crude oil was removed by distillation, and oxidized 15S (bright stock) extract oil 3' described in Example 1. Put it in a 300cc beaker,
Kaji Coal Oil C was obtained by floating for about 3 minutes using a rope machine equipped with a screw-type rotor.

On the other hand, for comparison, three oxidized 15-S (bright stock) extract oil obtained by liquid phase oxidation at a reaction temperature of 150° C. for 1 hour were mixed in the same manner as above to obtain mixed coal oil 〇. Furthermore, 100 yen of the pulverized charcoal and 100 yen of the pulverized oil were mixed in the same manner as described above to obtain charcoal oil ○ without the addition of a stabilizer. Table 2 shows the state of the obtained mixed coal oil after 3 weeks of standing still.

Example 3 Solve Tyler's 200 mesh strip. 100 pieces of pulverized anthracite coal that passed the 3% mark, and 100 pieces of oil made by removing the petroleum content of Iranian snake crude oil by distillation.
Oxidation #1 obtained by liquid-phase oxidation of #10 extract oil by-produced from the solvent refining equipment (furfural equipment) at an oil refinery at a reaction temperature of 150 oo for 4 hours.
0 extract oil 3 was placed in a 300 cc beaker and mixed for about 3 minutes using a rotor equipped with a screw-type rotor to obtain mixed coal oil E.

On the other hand, for comparison, 100 tons of the powdered coal and 100 tons of pulverized oil were mixed in the same manner as described above to obtain mixed coal oil F without the addition of a stabilizer. Table 2 shows the state of the obtained mixed coal oil immediately after it had been allowed to stand for three weeks.

Example: 86.3% of 4 tyler 200 mesh knots
Passed brown coal 100% fine coal and M with 1.9% sulfur content
/SC heavy oil emulsion (water addition amount: 5, [) 105] and 3 volumes of oxidized 15S (bright stock) extract oil described in Example 1 were placed in a 300cc beaker and heated to the top of a screw-type rotor. Mixed coal oil G was obtained by mixing the mixture for about 3 minutes using a mixing machine.

On the other hand, for comparison, the above-mentioned pulverized coal 100 nights and M/! SC heavy oil emulsion (water added amount: 5) 105' was mixed in the same manner as above, mixed coal oil without adding a stabilizer, and powdered coal 100 yen and M/SC heavy oil LO' were mixed in the same manner as above. A water-free mixed coal oil was obtained by mixing Nawahai. Table 3 shows the state of the obtained mixed coal oil after being heated at 70 qo for one week.

Example 5 A 200-mesh section of Tyler was spotted. Example 1
The oxidized 15-mass S (bright stock) extract oil 3 [described in 1. Ta.

On the other hand, for comparison, 100 pieces of the above-mentioned powdered coal and 105 pieces of MNOSC heavy oil emulsion (water addition amount: 5') were mixed in the same manner as above, and the mixed coal oil K and the mixed coal oil K with no stabilizer were mixed. Powdered coal 100g and M/SC heavy oil room' were mixed in the same manner as described above to obtain a water-free mixed coal oil L. Table 3 shows the state of the obtained mixed coal oil after heating and static layering at 70° C. for one week.

Table 2 Properties of peat oil Table 3 Properties of peat oil As is clear from Tables 2 and 3, the carburized oil of the present invention did not precipitate and solidify after aging, compared to the comparative example. You can see that it is excellent.

Claims (1)

[Scope of Claims] 1. Carboxyl groups obtained by oxidizing a hydrocarbon fraction having a boiling point of 200° C. or higher and containing 50% by weight or more of an aromatic carbon fraction are 0.0% per gram. A mixture of pulverized coal and hydrocarbon oil using oxidized oil containing 1 milligram equivalent or more as a stabilizer. 2. The mixture of pulverized coal and hydrocarbon oil according to claim 1, wherein an oxidized oil obtained by liquid-phase oxidation of an extract by-produced from a solvent refining device for a lubricating oil fraction is used as a stabilizer. 3 Using an emulsified hydrocarbon oil in which 2 to 100 parts by volume of water is mixed in advance with respect to 100 parts by volume of the hydrocarbon oil, the oil has a boiling point of 200°C or higher and contains an aromatic hydrocarbon fraction. A mixture of pulverized coal and emulsified hydrocarbon oil using as a stabilizer an oxidized oil of a hydrocarbon fraction containing 50% by weight or more. 4. The mixture of pulverized coal and emulsified hydrocarbon oil according to claim 3, wherein an oxidized oil obtained by liquid-phase oxidation of an extract by-produced from a solvent refining device for a lubricating oil fraction is used as a stabilizer.