JP2007031579A - Additive for water-solubilized heavy oil c, its production method and method for producing heavy oil c using the additive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enhance combustion efficiency of a heavy oil C by burning it efficiently through well mixing water in it. <P>SOLUTION: This method for producing water-solubilized heavy oil C comprises a step of preparing a 0.1-0.3% additive consisting of 56-64% 1-octanol, 23-18% polyphosphoric acid and 21-18% methanol, 10-20% water and a residuary untreated heavy oil C, a step of heating the untreated heavy oil C to a temperature higher than the following agitation temperature, a step of heating water to a temperature lower than the following agitation temperature, a step of mixing the additive in the heated water, and a step of adding the water mixed with the additive into the heated untreated heavy oil C to agitate at a fixed agitation temperature. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an additive in which C heavy oil and water are mixed to increase the combustion efficiency as water-solubilized C heavy oil, a method for producing the additive, and a method for producing water-solubilized C heavy oil using the additive About.

In recent years, attempts have been made to improve the combustion efficiency by mixing a suitable amount of water with heavy oil to produce a so-called emulsion fuel and combusting it.
However, conventional emulsion fuels are: 1. Corrosion of combustion chamber due to separation of water and oil 2. Decrease in thermal efficiency due to decrease in heat due to water. 3. Fuel consumption is reduced due to lower thermal efficiency. 4. Difficult to use at low load when starting with residual moisture 5. Necessity of special stirring device due to difficulty of water atomization; It had drawbacks and problems such as difficulty in stockpiling due to separation of water and oil.

Because of these factors, emulsion fuel has not been popularized in the market. In particular, factors such as reduced thermal efficiency, difficulty in stockpiling, and corrosion are major problems.
For example, Patent Document 1 discloses that water is mixed with kerosene, light oil, and A heavy oil to make a w / o emulsion fuel. However, this known technique cannot be applied to C heavy oil.
JP 2004-10765 A

  The present invention is intended to solve the above-mentioned problems. As a result of various researches and experiments, the knowledge that minimization of water fine particles in an emulsion fuel is an essential requirement primarily. Got. And based on the knowledge, this invention aims at providing the additive which can improve the combustion efficiency of C heavy oil, the manufacturing method of this additive, and the water-solubilized C heavy oil manufacturing method using this additive And

  The additive for water-solubilized C heavy oil according to the present invention is an additive for water-solubilizing C heavy oil in a volume ratio of 1-octanol 56% to 64%, polyphosphoric acid 23% to 18%, methanol 21% It consists of ~ 18%.

  In addition, the method for producing the additive for water-solubilized C heavy oil according to the present invention comprises mixing 1-octanol 56% to 64%, polyphosphoric acid 23% to 18%, and methanol 21% to 18% at room temperature. To obtain a mixture, to heat the mixture to 57 ° C. to 60 ° C. and to stand for at least 40 minutes, and then to stir the mixture to complete mixing.

  Moreover, the manufacturing method of the water-solubilization C heavy oil of this invention prepares the said additive for 0.1% -0.3%, 10% -20% water, and the remainder untreated C heavy oil. A step of heating untreated C heavy oil at a temperature higher than the stirring temperature described later, a step of heating water at a temperature lower than the stirring temperature described later, a step of mixing an additive into the heated water, And a step of adding water mixed with an additive to warm untreated C heavy oil and stirring at a predetermined stirring temperature.

  Moreover, the difference of the emitted-heat amount with respect to a theoretical value can be enlarged by selecting an additive in the range of 0.1%-0.2%.

According to the present invention, the combustion efficiency can be increased by a slight explosion of fuel.
The fuel itself has oxygen necessary for combustion, so that intake of combustion air can be suppressed during the combustion process, and a decrease in combustion gas temperature of the combustion engine can be suppressed.

Since the water droplets are nano-order, the contact area with the oil is increased, and the complete combustion of the fuel is promoted when the water slightly explodes during the inflammation process.
By complete combustion, the combustion gas heat escape and escape by unburned carbon (carbon) is reduced, and the residence time of the combustion gas is extended.

NO _x , CO, CO ₂ and PM are reduced in the exhaust gas from the environmental aspect, and NO _x , SO _x and PM can be reduced in the exhaust gas of C heavy oil.

Next, an embodiment of the present invention will be described.
The additive according to the present invention is to make a W / O state of C heavy oil / water mixing, that is, a so-called water-enclosed oil shape that is completely fused.

このように、界面活性剤分子は、親水性基と親油性基という二つの部分からなっている。親油基は、油と親合性を持ち、併せて疎水性を持ち、疎水基ともいう。親水基とは水に溶けやすい、あるいは混ざりやすい原子団のことである。油・水の混合液の中に、界面活性剤を入れると、界面活性剤が油・水の両界面に吸着しているため、その親水基と親油基によって、油・水をつなげて、その表面張力を弱め、その分離を防ぎ、油・水の完全融合をさせる。 A schematic diagram of the main structure of the additive is as follows.

Thus, the surfactant molecule consists of two parts, a hydrophilic group and a lipophilic group. The lipophilic group has affinity with oil and has hydrophobicity, and is also called a hydrophobic group. A hydrophilic group is an atomic group that is easily soluble or miscible in water. When a surfactant is placed in the oil / water mixture, the surfactant is adsorbed on both the oil and water interfaces, so the hydrophilic and lipophilic groups connect the oil and water, The surface tension is weakened, the separation is prevented, and the oil and water are completely fused.

  The additive for C heavy oil in the present invention is produced mainly from 1-octanol, polyphosphoric acid, and methanol, and these are used as follows.

1-octanol (Octanol, molecular formula: C ₈ H ₁₈ O, colorless and transparent liquid, specific gravity: 0.827, boiling point: 194.5 ° C., melting point: −17 ° C.) is soluble in ethanol, diethyl ether, etc., but is soluble in water Hateful. Oil products mainly consist of “—CH ₂ ... CH ₂ —”, but 1-octanol has “—CH ₂ ... CH ₂ —” (lipophilic group) similar to petroleum. By virtue of the principle that similar structures are acceptable to each other, they do not separate when contacted with oil, but rather have lipophilic properties and therefore function as lipophilic groups in the additive of the present invention.

The hydrophilic group portion effectively reduces the surface tension of water, and is exemplified as follows.

Polyphosphoric acid (polyphosphoric acid, molecular formula: H ₆ P ₄ O ₁₃ , molecular weight 337.97, melting point: 42 ° C., specific gravity: 1 liter ≈ 1.69 kg (specific gravity is considerably heavy), boiling point: 213 ° C.) is mixed with water Thus, various phosphoric acids can be formed as shown in FIG. Since -OPO ₃ ^2- contained is a hydrophilic group, it is used as a hydrophilic group in this additive.

There are also types such as 80% and 83% of the contained P ₂ O ₅ . As a result of testing various polyphosphorus, the above-mentioned kind has been successfully obtained as a hydrophilic group. The _P 2 _{O 5} is 80%, there was no significant difference even with either 83% of that.

Methanol (Metahanol, molecular formula: CH ₄ O, specific gravity: 1 liter≈0.79 kg, boiling point: about 64 ° C., melting point: −97 ° C., relative density: 0.792) is water, ethanol, diethyl ether (Diethyl ether) It is extremely soluble in water and can be dissolved in any ratio with water. Methanol is used as an antifoaming agent in this additive.

Next, the manufacturing method of the additive using the said component is demonstrated.
An additive is produced by mixing three components (a) 1-octanol, (b) polyphosphoric acid, and (c) ethanol at a predetermined volume ratio. An example is given below.
(1) At room temperature (15 ° C. to 28 ° C.), the three components are mixed in a volume ratio of (a) 60%, (b) 20%, (c) 20% (in this specification, in principle, volume) The ratio is written in the ratio, and the weight ratio is written down). The order of mixing is (c), (a), (b) in terms of specific gravity, but the order can be changed.
(2) The mixture in a state where the above three components are mixed is heated to 57 ° C. to 60 ° C., is not stirred, and is kept at this temperature for a minimum of 40 minutes.
(3) After heating to 57 ° C to 60 ° C, the raw materials start to mix after 3 to 5 minutes.
(4) Polyphosphoric acid begins to light yellow in 20 to 25 minutes after heating.
(5) After heating, the light yellow layer at the bottom gradually increases in thickness from 35 to 40 minutes later.
(6) After stirring for 40 to 50 minutes after heating, the light yellow layer spreads throughout and the color increases in intensity, and finally an additive in which the above three components are completely fused and mixed is obtained. .
The finished additive does not deteriorate in quality between -15 ° C and + 40 ° C, does not deteriorate for about 3 months when stored at high temperature (50 ° C to 90 ° C), and does not deteriorate for about 2 years when stored at room temperature It was.

  When the ratio of the additive was changed and the production experiment of water-solubilized C heavy oil was conducted as described later, when 1-octanol was less than 56%, oil separation was observed, and when polyphosphoric acid was less than 23%, water separation was achieved. It was recognized that foaming was observed when methanol was less than 21%. On the other hand, when 1-octanol exceeds 64%, polyphosphoric acid exceeds 18%, and methanol exceeds 18%, the functions of the other two components are suppressed. Therefore, by combining these, 1-octanol 56% to 64%, polyphosphoric acid 23% to 18%, and methanol 21% to 18% are ideal mixing ratios.

Next, an example of a method for producing a C heavy oil / water mixture, that is, a water-solubilized C heavy oil, using the additive produced as described above will be described.
Prepare 3 components of 10% water, 0.1% of the additive produced as described above, and the remaining C heavy oil, and mix these in the following steps to produce water-solubilized C heavy oil. To do.

(1) The untreated C heavy oil based on the ratio is heated and maintained at a flow temperature higher than the stirring temperature described later, preferably 75 ° C. to 85 ° C. to improve the fluidity.
(2) Water containing the additive is heated to a temperature lower than the stirring temperature of 65 ° C. described below, preferably 50 ° C. to 60 ° C., and the temperature is maintained. After warming, add the additive based on the ratio and stir for 5-10 minutes.
(3) When the above process is completed, confirm that the temperature of the untreated C heavy oil has dropped to 65 ° C., add water containing the additive, and immediately stir. The stirring time is at least 30 minutes to 40 minutes. A stirrer that can be heated is used, and the stirring temperature is 55 ° C. <C heavy oil + additive water <60 ° C.
(4) During the stirring, pay close attention to keeping the temperature between 50 ° C and 60 ° C. Below 55 ° C, the viscosity of C heavy oil increases and water and oil do not mix well. Moreover, when it exceeds 60 degreeC, since the boiling point of one evaporation temperature methanol of a raw material is 64 degreeC, the efficacy of an additive will be lost.
(5) When stirring, cover the container to prevent evaporation of one of the raw materials.
A water-solubilized C heavy oil is obtained by the above steps.

  A photograph of the water-solubilized C heavy oil produced as described above (photographing equipment is an Olympus biological microscope made in Japan) is shown in FIG.

  As shown in FIG. 1, water (inside white circle) has a size of 100 nm to 300 nm and is evenly scattered in the oil droplets. That is, it is in a state where oil is covered and wrapped around the water, that is, it is a W / O type.

  The boiler combustion experiment of the water-solubilized C heavy oil manufactured as mentioned above was conducted, and the calorific value was measured. The additive comprising the above three components was added at a volume ratio of 0.1%, water 20% to 30%, and the balance was C heavy oil.

表１に示されるように、理論熱量に対し、水可溶化Ｃ重油の熱量の優位性は、水１０％〜２０％で顕著である。この結果は図２に示されている。
図２において上側の４本の線、試料１〜４は実質的に同一の性質を示しており、下側の添加剤を添加しない場合と著しく異なっている。

As shown in Table 1, the superiority of the calorific value of the water-solubilized C heavy oil with respect to the theoretical calorific value is remarkable at 10% to 20% of water. The result is shown in FIG.
In FIG. 2, the upper four lines, samples 1 to 4, show substantially the same properties, and are markedly different from the case where the lower additive is not added.

When frying up an example of theoretical calorific value calculation (water 10%) in the table,
(0.931 * 9) + 1/10 = 0.938 (Density x Fuel ratio) + Water ratio / 10 = A
43,061 * 0.9 * 0.931 = 36,080 Calorie x Fuel ratio x Density = B
36,080 / 0.938 = 38,465 B ÷ A = theoretical calorie In addition, when measuring the calorific value of the finished product in the above table, the water-solubilized C heavy oil is measured not by volume but by weight. This is a more accurate measure of heat.

表に示されるように、添加剤０．１％、０．２％、０．３％の添加で、水１０％〜２０％の範囲において、Ｃ重油の燃焼熱量が理論値を上回っており、特に添加剤０．１％、０．２％がより高い燃焼効果を発揮する。
図３は表２をグラフとして示している。そして線Ａは添加料０．２％、線Ｂは添加料０．１％、線Ｃは添加料０．３％、線Ｄは無添加の場合を示している。 Next, combustion calorimetry of additives 0.1% to 0.3%, water 0% to 22%, and the balance C heavy oil was measured. The results are shown in Table 2.

As shown in the table, with the addition of 0.1%, 0.2%, and 0.3% additives, the combustion heat of C heavy oil exceeds the theoretical value in the range of 10% to 20% of water, In particular, the additives 0.1% and 0.2% exhibit a higher combustion effect.
FIG. 3 shows Table 2 as a graph. Line A shows an additive 0.2%, line B shows an additive 0.1%, line C shows an additive 0.3%, and line D shows no additive.

Furthermore, the result of having measured the emitted-heat amount by combustion experiment is shown to Tables 3-8.
As shown in Tables 3 and 4, the calorific value in the case of 0.1% additive is much higher than the theoretical value, and the difference in calorific value between Table 3 and Table 4 is as shown in Table 5. It was.
As shown in Tables 6 and 7, the calorific value in the case of 0.2% additive is much higher than the theoretical value, and the difference in calorific value between Table 6 and Table 7 is as shown in Table 8. It was.

この表４はグラフとして図４に示されている。

この表５はグラフとして図５に示されている。

Table 4 is shown in FIG. 4 as a graph.

Table 5 is shown as a graph in FIG.

この表７はグラフとして図６に示されている。

Table 7 is shown in FIG. 6 as a graph.

  As described above, the calorific value of the water-solubilized C heavy oil according to the present invention is much larger than the theoretical value, and the combustion efficiency can be improved. The combustion phenomenon will be described next.

1. Water-solubilized C heavy oil has water particles that are nano-sized and water particles are averagely distributed in the oil, increasing the heavy oil from becoming a mist. This increases the surface area of the oil. Therefore, the contact area with oxygen in the air increases, and the combustion efficiency increases.
2. During combustion, when the temperature of the oil covering the water with the W / O type increases, the water vaporizes instantaneously and a micro explosion occurs. Thereby, the phenomenon which makes oil a mist state increases. In addition, the molecular level of water reacts with oxygen, avoiding incomplete combustion of the oil and increasing the combustion efficiency of the oil.
3. The slight explosion of oil increases the thermal conductivity of oil and water. As a result, the heat consumption rate is reduced, and as a result, the combustion efficiency is increased, leading to oil saving.
4). It is speculated that the water in the oil may have caused a chemical reaction, increasing the combustion efficiency.

The enlarged photograph of the water-solubilization C heavy oil by this invention. The figure which shows Table 1 as a graph. The figure which shows Table 2 as a graph. The figure which shows Table 4 as a graph. The figure which shows Table 5 as a graph. The figure which shows Table 7 as a graph.

Claims (3)

Additive for water solubilization of C heavy oil, water solubilization characterized by comprising 1-octanol 56% to 64%, polyphosphoric acid 23% to 18%, methanol 21% to 18% by volume ratio C heavy oil additive. A step of mixing 1-octanol 56% to 64% by volume, polyphosphoric acid 23% to 18%, and methanol 21% to 18% at room temperature to obtain a mixture, and the mixture at 57 ° C to 60 ° C The method for producing an additive for water-solubilized C heavy oil according to claim 1, comprising a step of heating and allowing to stand for at least 40 minutes, and then a step of stirring the mixture to complete mixing. The step of preparing 0.1% to 0.3% of the additive according to claim 1, 10% to 20% of water, and the remaining untreated C heavy oil, and the untreated C heavy oil from the stirring temperature described later A step of heating at a high temperature, a step of heating water at a temperature lower than the stirring temperature described later, a step of mixing an additive in the heated water, and an additive in the heated untreated C heavy oil A method for producing water-solubilized C heavy oil, comprising a step of adding mixed water and stirring at a predetermined stirring temperature.

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