JP2008255208A - Additive for water-solubilized oil, method for producing the same additive, and method for producing water-solubilized oil by using the same additive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive for water-solubilized oil in which combustion state is improved and combustion efficiency is enhanced by mixing an oil such as heavy oil A with water. <P>SOLUTION: The additive for water-solubilized oil for mixing an oil such as heavy oil A with water comprises 71.3-66.5 wt.% oleic acid, 3.2-3.8 wt.% fatty acid diethanol amide, 11.0-13.1 wt.% methanol, 2.5-3.2 wt.% 2-aminoethanol, 6.5-7.2 wt.% cyclohexylamine and 5.5-6.2 wt.% ammonia. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an additive for water-solubilized oil, and more particularly to an additive for water-solubilized oil in which oil such as A heavy oil or light oil is mixed with water to make it water-soluble oil to increase its combustion efficiency. The present invention also relates to a method for producing the additive and a method for producing a water-solubilized oil using the additive.

  In recent years, from the viewpoint of reducing the environmental load of exhaust gas emitted when burning fossil fuels such as light oil and heavy oil, so-called emulsion fuels in which an appropriate amount of water is mixed with these fuels have been actively studied. .

  However, conventional emulsion fuels are: 1. Stockpiling and transportation difficulties due to short-term separation of water and oil; 2. Reduction of combustion temperature due to heat reduction by water; 3. Fuel consumption is reduced due to lower thermal efficiency. 4. Difficult to use at start-up or low load due to residual moisture. 5. Necessity of a special stirring device (eg, heating, pressurization, etc.) due to difficulty in water atomization; It had drawbacks and problems such as corrosion of the combustion chamber due to separation of water and oil.

Because of these factors, emulsion fuel has not been popularized in the market. For example, the present applicant has previously proposed making an emulsion fuel in which water is mixed with C heavy oil (Patent Document 1). However, although this known technique has many advantages such as excellent combustion efficiency and stockpiling, it is difficult to apply to oils other than C heavy oil.
JP 2007-31579 A

  The present invention is intended to solve the above-mentioned problems. As a result of various researches and experiments, the water is mainly caused by minimization of water particles in a water-oil mixed fuel, that is, an emulsion fuel. And the fusion of oil is an absolute requirement. And based on that knowledge, the present invention provides an additive capable of uniformly mixing and fusing oil and water to increase its combustion efficiency, a method for producing the additive, and a water-soluble oil producing method using the additive. The purpose is to provide.

  The additive for water-solubilized oil of the present invention is an additive for water-solubilized oil for mixing oil such as heavy oil A with water, 71.3% to 66.5% oleic acid by weight ratio, diethanolamine fatty acid 3.2% to 3.8%, 11.0% to 13.1% methanol, 2.5% to 3.2% 2-aminoethanol, 6.5% to 7.2% cyclohexylamine, and ammonia Including 5.5% to 6.2%.

  In the method for producing an additive for water-solubilized oil of the present invention, 71.3% to 66.5% by weight of oleic acid is placed in a stirrer, and 3.2% to 3.8% of fatty acid diethanolamide by weight. % In a stirrer and stirring and mixing, methanol in a weight ratio of 11.0% to 13.1% in a stirrer and stirring and mixing, and then 2-aminoethanol in a weight ratio of 2 A step of stirring and mixing 5% to 3.2% in a stirrer, a step of stirring and mixing cyclohexylamine 6.5% to 7.2% in a stirrer, and 5.5% to 6.2% of ammonia % In a stirrer and stirring and mixing.

  The method for producing water-solubilized oil of the present invention is prepared by preparing 10% to 3%, 10% to 32% water, and the remaining untreated A heavy oil in the volume ratio. And a step of stirring and mixing them.

  The method for producing a water-solubilized oil of the present invention comprises a step of preparing 10% to 7%, 10% to 28% water, and the remaining untreated gas oil as the water-solubilized oil additive, And stirring and mixing.

  (1) With the additive for water-solubilized oil of the present invention, water particles can be instantly minimized to 80 to 120 nm, and the minimized water can be uniformly distributed in the oil by stirring. Can be dispersed.

  (2) As a result, water molecules can be completely encapsulated with oil molecules, and unlike conventional emulsion fuel, water can be completely dissolved in oil.

  (3) The water-solubilized oil produced by using the additive of the present invention, that is, the oil / water mixed fuel, has transparency, so that water and oil are separated even if left for a long time (several years). Very stable without.

  (4) The biggest cause of separation of water and oil is that the surface tensions of the two are extremely different. If the additive of the present invention is used, the surface tension of water and oil should be almost the same. As a result, separation of water and oil can be prevented.

  The water-solubilizing additive of the present invention is as described above. First, the production method will be described.

  The oleic acid (Oleic Acid) which is the main component of the water-solubilizing additive of the present invention is placed in a stirrer with 71.3% to 66.5% by weight of the additive, and then coconut fatty acid diethanolamide (Coconuts Diethanol Amide). ) In a weight ratio of 3.2% to 3.8%, and the mixture is stirred for 8 to 12 minutes.

  Arbitrary and publicly known stirrers are used. In this production method, for example, three propellers arranged in a diameter direction are placed in a container having a bottom portion formed in a funnel shape with a vertical cylindrical container having a diameter of 1 m and a height of 1.5 m, and capable of accommodating about 1000 liters of liquid. A stirrer provided in upper and lower three stages was used. The stirring speed was 120 to 200 revolutions per minute depending on the height of the freezing point of oleic acid.

  Next, methanol (Methanol) is added at a weight ratio of 11.0% to 13.1%, and then stirred and mixed for 18 to 20 minutes.

  After the stirring is completed, the mixture is stirred and mixed with 2-aminoethanol (Monoethanolamine) in a weight ratio of 2.5% to 3.2%. At this time, heat generation starts after the start of mixing, but it is important to add small amounts while suppressing the heat generation to 45 ° C or lower. After the entire amount is added, the mixture is stirred for about 13 to 17 minutes.

  Next, cyclohexylamine (Cyclohexylamine) is added in a weight ratio of 6.5% to 7.2% and stirred. At this time, heat generation starts immediately after mixing, but the heat generation is mixed little by little while suppressing the heat generation to 40 ° C. or less. The stirring time is 13 to 17 minutes.

  Subsequently, ammonia (Ammonium hydroxide) is mixed in 5.5 to 6.2% by weight. At this time, heat generation starts rapidly after mixing, but it is important to add small amounts while keeping the heat generation at 45 ° C or lower. While stirring, a bubble-like substance similar to a bubble-like substance is generated, but the bubble-like generation means the progress of a chemical reaction, and this disappearance means the end of the reaction.

  After this “bubble-like” disappears, stir for 35 to 50 minutes, and finish slowly.

Stirring speed before disappearance of “bubbles”: 150 rpm / min to 200 rpm / min, stirring speed after disappearance of “bubbles”: 50 rpm / min to 60 rpm / min, When the liquid temperature is 35 ° C. or lower after the final process is completed, the process is completed.

  The stirrer is not limited to 1000 liters, and can be modified by using one propeller in a 50 liter container or two propellers in a 50 liter to 1000 liter container.

The main properties of the raw materials which are the six kinds of components used in the present invention are as follows.
(1) Oleic acid (Oleic Acid. Molecular formula: C18H34O2) ... Molecular weight: 282.45-282.52. Specific gravity (25 ° C.): 0.8905 to 0.898. Flash point (° C): 189. Boiling point (° C): 215-360. Ignition temperature (° C): 36 3. Melting point (° C): 6-16. Appearance: colorless liquid in the pure state. However, if it is not pure, it is a pale yellow or reddish brown oily liquid. Fatty acids contained in animals and plants. ) Is the main component of the oil / water solubilizing additive of the present invention. Insoluble in water. A freezing point of 8 ° C. or lower is preferred.

  (2) Coconuts Diethanol Amide ... Molecular formula C16H35NO3. Nonionic surfactant. Used as thickening foaming agent, low temperature stabilizer. Physical properties: viscous yellow liquid. Melting point: <10 ° C. Boiling point: 169-275. Specific gravity: 0.99. PH: 9 (1% SOL). Solubility: Water soluble. Flash point:> 100 ° C. It is more widely used as a cleaning agent than a surfactant. In addition to detergency, it has the properties of low foam and chemical stability.

  (3) Methanol ... Molecular formula: CH4O. Density (20 ° C.): 0.791-0.792. Boiling point (° C): 64.0-65.5. Distillation volume (milliliter): 98 or more. -Temperature range: 0.8. Water content: 0.1. Appearance: colorless and transparent liquid. Water soluble. It can be dissolved in any ratio with water.

  (4) 2-aminoethanol (Monoethanolamine) Molecular formula: C2H7NO. Molecular weight: 61.08. Properties: Viscous liquid. Specific gravity: 1.0179 (2C / 4 ° C). Boiling point: 70.5 (760 mmHg). Melting point: 10.3 ° C. Appearance: viscous liquid. Applications: Synthetic detergents, emulsifiers, neutralizers.

(5) Cyclohexylamine ... Molecular formula: C6H13N. Molecular weight: 99.17. Density: 0.867. Boiling point (° C): 134. Melting point: -17.7 ° C. Flash point = 31 ° C. Ignition point = 293 ° C. Properties: Colorless. Liquid with strong amine odor. Completely soluble in most organic solvents such as water and ethanol. Application: Used as a "crosslinking agent", dyeing aid, antifreeze, dye material, surfactant material, etc. when manufacturing rubber products such as tires. In addition, it is used as a corrosion inhibitor.

(6) Ammonium hydroxide ... Molecular formula: NH4OH. Properties: Colorless and transparent. Specific gravity: (d25 ° C./25° C.): 0.90. Content: 25%. It dissolves very well in water. Acts as a nucleophile in organic reactions, promotes and strengthens binding.

  According to the above production method, 71.3% to 66.5% oleic acid, 3.2% to 3.8% fatty acid diethanolamide, 11.0% to 13.1% methanol, 2-aminoethanol. Additives are made containing 5% to 3.2%, cyclohexylamine 6.5% to 7.2%, and ammonia 5.5% to 6.2%.

  The mixing ratio of the six components of the additive will be described. When oil / water-solubilized fuel is produced using the additive (the production method will be described later), if the oleic acid exceeds 71.3% by weight, the progress of emulsification slows down, and the functions of the other five components In addition, if it is less than 66.5%, sufficient emulsification cannot be achieved.

Further, when the fatty acid diethanolamide exceeds 3.8%, the change in the surface tension of water and oil is slowed down, and when it is less than 3.2%, the change in the surface tension is insufficient. Moreover, when methanol exceeded 13.1%, the change of the surface tension of water and oil slowed down, and when less than 11.0%, the change of surface tension was insufficient.
When the amount of 2-aminoethanol exceeds 3.2%, the increase in the binding force of water molecules slows down, and when the amount is less than 2.5%, the binding force is insufficient.

When the amount of cyclohexylamine exceeds 7.2%, the modifying action of the additive is slowed down, and when it is less than 6.5%, the modifying action of the additive is insufficient.
If ammonia exceeds 6.2%, the ester action of methanol slows down, and if less than 5.5%, the ester action of methanol is insufficient.

  Next, a method for producing a water-solubilized oil, which is an oil / water mixed fuel, using the additive produced as described above will be described.

  First, an oil for mixing the additive and water is prepared. The oil targeted by the additive of the present invention is A heavy oil, light oil, etc., and water can be mixed with these oils.

  First, the additive produced as described above is mixed into the oil and agitated by the same agitator as that for the additive production. The stirring time is 15 to 25 minutes at 80 to 120 rpm. It is important that the additive is evenly and evenly applied in the oil, so that water added thereafter can be dissolved in the oil, but stirring is an important step.

  Next, water is added to the oil to which the additive of the present invention has been added and stirred well. The stirring time is preferably 40 to 60 minutes at 120 to 160 revolutions / minute. Immediately after the water is added, the water layer is separated into the lower layer and the oil layer is separated into the upper layer. However, by stirring, the water is completely solubilized in the oil through the emulsion state (emulsified state), and transparency is improved. An oil / water mixed fuel is produced.

  The additive of the present invention is not particularly limited with respect to the type of water such as hard water and soft water, and normal tap water and well water can be used.

  The blending ratios of oil, water and the additive of the present invention are slightly different depending on the type of oil. When A heavy oil is used as the oil, they are mixed in a volume ratio of A heavy oil: water: additive = 80: 10: 10 to 65: 32: 3.

  The mixing ratio in the case of A heavy oil is as described above, and the maximum mixing ratio of the additive is 10%. The amount of combustion heat as a water-solubilized fuel is suppressed, and if the minimum ratio is less than 3%, the mixed emulsification of oil and water becomes incomplete. For the following various oils, the mixing ratio of oil: water: additive is determined in the same manner.

  Moreover, when using light oil as oil, it mixes in the ratio of light oil: water: additive = 80: 10: 10-65: 28: 7 by each volume ratio.

  When the capacity of the stirring tank is 50 liters or less, the number of propellers to be stirred may be one, but when the capacity exceeds 50 liters, it is preferable to have at least two propellers. If the tank capacity exceeds 1000 liters, it is better to have three propellers.

  When mixing with water, it is easier to mix water when sprayed as much as possible. It is preferable to spray water on the oil / additive mixture using, for example, a shower.

  The experimental results of various water-solubilized oils produced with the additive of the present invention will be described below.

  Table 1 shows a comparison of combustion experiments between the conventional fuel using A heavy oil and the water-solubilized fuel of the present invention. Compared with conventional fuels, the water-solubilized fuel according to the present invention has a high combustion efficiency and combustion value / heavy oil amount, a small amount of environmentally hazardous substances discharged, and a price / volume which is a fixed price.

表１はエマルジョン燃料（前記特許文献１参照）と本発明の水可溶化燃料の燃焼比較を示すものである。

Table 1 shows the combustion comparison between the emulsion fuel (see Patent Document 1) and the water-solubilized fuel of the present invention.

この表から解るように、本発明による水可溶化燃料はエマルジョン燃料に比して、価格／体積は高めであるが、燃焼効率、燃焼値／体積、燃焼値／重油量、備蓄可能性、燃焼機関の腐食可能性において極めて優れている。

As can be seen from this table, the water-solubilized fuel according to the present invention is higher in price / volume than the emulsion fuel, but the combustion efficiency, combustion value / volume, combustion value / heavy oil amount, reserve possibility, combustion Excellent in corrosion potential of the engine.

Next, Tables 3 and 4 show examples of boiler combustion tests.

  The above test is an example of the fire burning test of the firewood shiitake cultivation association. The date, place, etc. are as follows: December 21-22, 2006 (19: 00-23: 00), Place: Nagasaki Prefecture Shimabara-shi, boiler used: Kokata Iron Works hot water boiler Maximum: 6,500 calories / H, fuel used: A heavy oil, emulsion fuel (75% A heavy oil, 20% water, 5% additive).

  The column 29 in Table 3 corresponds to the number of ignitions and standbys, and the column 9 in Table 4 corresponds to the number of ignitions and standbys. The virgin in Table 3 represents a normal virgin A heavy oil, that is, an untreated A heavy oil, and the hydrous fuel in Table 4 represents the water-solubilized oil of the present invention. These tables are shown graphically in FIGS.

  As can be seen from Tables 3 and 4 and FIGS. 1 and 2, ordinary virgin A heavy oil, that is, untreated A heavy oil, repeatedly ignites and extinguishes a total of 29 times within the same 4-hour combustion time as conventional emulsion fuel. . In addition, the boiler installed in this shiitake cultivation room is controlled to extinguish when the room temperature reaches a higher set temperature and to reignite when the room temperature reaches a lower set temperature.

  On the other hand, the water-solubilized oil of the present invention shown as a hydrous fuel in Table 4 has a total of nine ignition and extinguishing times during the same four hours. That is, the water-solubilized oil of the present invention has a long indoor temperature warming time, but also a long cooling time (waiting time until the next ignition), and keeps the indoor temperature high by a small number of times of ignition and extinguishing. Can do.

  Further, in the case of virgin A heavy oil, the combustion time next to the standby time tends to be longer than the previous standby time except for a part. On the other hand, in the case of hydrous fuel, that is, the water-solubilized oil of the present invention, the reverse phenomenon occurs that the next combustion time is shorter than the standby time, and the combustion efficiency of the present invention is superior. It can be said that

  Next, experimental results in a diesel engine using light oil and the water-solubilized light oil fuel of the present invention will be described.

The test engine and generator used in the experiment are Yanmar generator YDG2000, and the specifications are as follows.
The specifications of the diesel engine are: model: 4-cycle vertical air-cooled diesel engine, combustion system: direct injection system, displacement: 199cc, compression ratio: 20.5: 1. The specifications of the generator are: Model: Single phase, Self-excited, Rotating field type, Number of poles / Power factor: 2.1.0, Rated output / Maximum output: 1.7 kW / 2.0 kW (100 V), Rated Rotational speed: 3600 rpm.

  Table 5 below compares the engine performance, exhaust gas performance, and 5.7% water-containing light oil fuel data at the regular injection timing of light oil. The load is data for a standard rated output of 1.7 kW.

  Table 5 shows a comparison of fuel injection timing and engine and exhaust gas performance when using light oil / water-solubilized light oil fuel. In Table 5, “light oil-” represents normal light oil without additives, and “moisture content— "Indicates a water-solubilized gas oil fuel according to the present invention.

As shown in Table 5, the following remarkable effects are observed.
(1) The fuel consumption rate is the fuel consumption weight g when the engine is operated for 1 hour at a rated output of 1.7 kW. This fuel consumption weight is about 6.8% higher than diesel oil from 395/370 = 1.0676. The calorific value of each fuel is 45,000 J / g of light oil, 41,663 J / g of water-containing light oil, and if the same amount of heat as that of light oil is given to the engine with water-containing light oil, 45,000 / 41,663 = 1.080. The fuel weight increases by about 8.0%. Therefore, the increase in fuel heat generation is 8%, while the experimental result is only 6.8% increase, and the hydrous diesel oil has improved engine combustion efficiency, that is, thermal efficiency.

(2) The thermal efficiency is 21.9% for diesel oil-21.6% of regular injection timing, and 21.9% for water-containing diesel oil-5.5 ° advance angle. The thermal efficiency is improved by about 1.4%.
Incidentally, in terms of engineering, thermal efficiency is the ratio between the engine work of the rated output and the heat amount of the fuel consumed for the work in the case of rated output operation. Therefore, about 22% of the consumed fuel heat amount is used as an effective work of the engine, and most of the heat amount 78% is lost heat amount such as exhaust gas, cooling loss and friction loss. The experiment for changing the fuel injection timing, combined with the effect of the water of the hydrated fuel, tries to convert the amount of heat generated by the combustion of the fuel as much as possible into the effective work of the engine.

(3) The fuel consumption rate and the thermal efficiency are characteristics related to the fuel weight, but the fuel injection amount represents the fuel consumption volume mm3 / st during rated operation. The unit st is the combustion stroke of the engine. That is, in rated operation, in the case of a four-cycle engine, one revolution is injected into two revolutions of the engine. The fuel volume is mm3. Compared to 7.00 mm 3 / st of light oil, the water-containing light oil is 7.39 mm 3 / st, which is about 5.6% larger than 7.39 / 7.00 = 1.0557. As described above, the fuel injection amount is increased by about 5.8% from the relationship of the heat generation amount per volume, and the effect of improving the thermal efficiency is exhibited.

  (4) The exhaust gas temperature is 305 ° C for water-containing gas oil, compared to 336 ° C for light oil. A decrease in exhaust gas temperature indicates that the amount of heat lost in exhaust gas decreases, which means an improvement in thermal efficiency. For example, in the case of increasing the engine output by increasing the compression ratio in a gasoline engine, improving the combustion pressure raises the combustion gas temperature and conversely lowers the exhaust gas temperature. Therefore, if the fuel injection timing is advanced by 5.5 ° when using hydrous light oil, it is considered that the improvement of the combustion pressure raises the combustion gas temperature and the exhaust gas temperature decreases conversely.

The experimental results of the diesel engine can be summarized as follows.
Diesel engine combustion is combustion of light oil droplets, and fuel vaporized by physical phenomena and oxygen in the air form a mixture on the surface of the fuel droplets and burn with various excess air ratios. At this time, the water particles contained in the droplets are also heated by receiving the radiant heat due to this combustion, reach the boiling point, undergo micro explosions one after another, and secondary atomization occurs by scattering the surrounding oil enemies. In this way, when the oil is instantly atomized, the contact area with the air is increased, complete combustion is rapidly performed, and generation of smoke and unburned carbon in the combustion exhaust gas is suppressed.

Further, this increase in the contact area can keep the excess air necessary for combustion low, so the energy saving effect is increased.
In order to satisfy this condition, micronization of water particles is the most important, but since normal water particles have a large surface tension, it is difficult to micronize water particles.

  In the present invention, because of the additive mainly composed of oleic acid, it becomes possible to micronize water particles to the limit, and at the same time, it is not simply a mixture of oil and water, but water is in a state of being soluble in oil, so that it can be used for a long time. Stockpile is now possible.

  Although the present invention has been described above, the present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. It is included in the technical scope.

FIG. 3 is a graph of Table 3. The figure which made Table 4 a graph.

Claims (4)

In an additive for water-solubilized oil for mixing oil such as heavy oil A with water, 71.3% to 66.5% oleic acid, 3.2% to 3.8% fatty acid diethanolamide, and methanol by weight Contains 11.0% to 13.1%, 2-aminoethanol 2.5% to 3.2%, cyclohexylamine 6.5% to 7.2%, and ammonia 5.5% to 6.2%. An additive for water-solubilized oils. A step of mixing 71.3% to 66.5% by weight of oleic acid in a stirrer and 3.2% to 3.8% of fatty acid diethanolamide in a stirrer and stirring and mixing, followed by methanol 11.0% to 13.1% by weight ratio in a stirrer and stirring and mixing, and then 2-aminoethanol 2.5% to 3.2% by weight in a stirrer and stirring and mixing A step of putting 6.5% to 7.2% of cyclohexylamine in a stirrer and stirring and mixing, and a step of stirring and mixing 5.5% to 6.2% of ammonia in a stirrer. The method for producing an additive for water-solubilized oil according to claim 1. In a volume ratio, the step of preparing 10% to 3% of the additive for water-solubilized oil of claim 1, 10% to 32% of water, and the remaining untreated A heavy oil, and stirring and mixing them A process for producing a water-solubilized oil, comprising: a step. In a volume ratio, the step of preparing the water-solubilizing oil additive of claim 1 with 10% to 7%, 10% to 28% water, and the remaining untreated light oil, and the step of stirring and mixing them A method for producing a water-solubilized oil, comprising:

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