JP2018135403A - Liquid fuel and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide liquid fuel having higher combustion efficiency and yielding a smaller amount of exhaust relative to conventional nano emulsion fuel.SOLUTION: There is provided liquid fuel having higher combustion efficiency and yielding a smaller amount of exhaust relative to conventional one, which fuel is obtained by blending heavy oil with water and CD (cyclodextrin) to produce a suspension of oil and water.SELECTED DRAWING: None

Description

  The present invention relates to a liquid fuel. More specifically, the present invention relates to a liquid fuel in which heavy oil, water and cyclodextrin are mixed to form a suspension. The present invention also relates to a method for producing the liquid fuel.

  Conventionally, petrochemical fuels and emulsion fuels have been used in thermal power plants, industrial boilers, and the like. An emulsion fuel is a fuel in which water and an emulsifier (surfactant) are mixed with a petrochemical fuel to form a water emulsion in an oil phase (see, for example, Patent Documents 1 and 2). Could not be raised sufficiently, and there were many problems such as low-temperature safety (separation).

Therefore, in recent years, in the production of emulsion fuels, mineral oil that has been aerated with heated compressed air for a certain period of time and mixed with water and vegetable oil activated by increasing the pH, or similarly aerated by cutting off the hydrocarbon chain, etc. And a method of stirring and mixing water activated by breaking hydrogen bonds (see, for example, Patent Documents 3 and 4).
Also, while adding water to the flammable oil, refinement and mixing means to make water or an emulsion fuel with an average particle size of the flammable oil of 1000 nm or less, or mix the oil or water subjected to plasma discharge. A method for producing an emulsion fuel has been developed (see, for example, Patent Documents 5 and 6).

The present inventors have also used a liquid fuel obtained by suspending ionized water obtained by energizing purified soft water and petrochemical fuel, and a nanobubble machine when suspending petrochemical fuel, water and oxygen. We are developing liquid fuels obtained by dispersing (see, for example, Patent Documents 7 to 9), and applying ozone generation technology in air discharge to liquid discharge to dissociate water, Nanoemulsion fuels are being developed by partially decomposing carbon bonds.
Such an emulsion fuel is called a nanoemulsion fuel or the like, and has an advantage that combustion efficiency is higher than that of a conventional emulsion fuel. However, it is desired to provide a liquid fuel with higher combustion efficiency and a reduced amount of exhaust gas such as NOx, SOx, and CO ₂ .

In the present invention, the present inventors paid attention to cyclodextrin (CD) (hereinafter sometimes simply referred to as CD). CD is a kind of cyclic oligosaccharide in which D-glucose is bonded by α (1 → 4) glucoside bond and has a cyclic structure, and is used for various substances such as foods, detergents and deodorants.
CD is also used as a fuel for fuel cells, and it is also disclosed that it is used as a support for fixing methanol, which is a liquid fuel, or combined with a benzyl alcohol derivative (see, for example, Patent Documents 10 and 11). .
However, it has not been known to use CDs for the production of liquid fuels that require high combustion efficiency, such as those for thermal power plants and industrial boilers.

JP 2014-159538 A JP 2003-221484 A JP 2009-286884 A JP 2010-1000075 A1 JP 2008-81740 A JP 2007-224156 A JP 2009-256501 A JP 2013-18867 A Korean Patent No. 10134497 Japanese Patent Laid-Open No. 2006-156086 JP 2005-79955 A

  An object of the present invention is to provide a liquid fuel having a high combustion efficiency and a reduced exhaust gas amount as compared with a conventional nanoemulsion fuel.

  As a result of intensive studies in providing the liquid fuel, the present inventors have obtained a combination of CD in the nanoemulsion fuel production method developed by the present inventors, and a mixture of heavy oil with water and CD to obtain a suspension. It has been found that the liquid fuel is a liquid fuel having a higher combustion efficiency than the conventional liquid fuel and the amount of exhaust gas is reduced, and the present invention has been completed.

That is, the present invention relates to the following liquid fuel and a manufacturing method thereof.
[1] A liquid fuel in which heavy oil, water and cyclodextrin are mixed to form a suspension.
[2] The liquid fuel according to [1], wherein the heavy oil is one or more of A heavy oil and C heavy oil.
[3] The cyclodextrin is hydroxypropyl-β-cyclodextrin (HP-β-CD), hydroxypropyl-α-cyclodextrin (HP-α-CD), hydroxypropyl-γ-cyclodextrin (HP-γ-CD) ) Or β-cyclodextrin (β-CD), the liquid fuel according to the above [1] or [2].
[4] The liquid fuel according to any one of [1] to [3], wherein the cyclodextrin is added at 0.005 w / w% to 5.0 w / w%.
[5] The liquid fuel according to any one of [1] to [4], wherein the water is added at 1.0 v / v% to 50.0 v / v%.
[6] The method for producing a liquid fuel according to any one of the above [1] to [5], comprising a step of passing a mixture of heavy oil, water and cyclodextrin under pressure through a fine gap.
[7] Hydroxypropyl-β-cyclodextrin (HP-β-CD), hydroxypropyl-α-cyclodextrin (HP-α-CD), hydroxypropyl-γ-cyclodextrin (HP-γ-CD) or β- A fuel oil and / or water nano-promoter containing any one or more of cyclodextrins (β-CD).

  The liquid fuel of the present invention is a liquid fuel that exhibits a special effect that combustion efficiency is higher than that of conventional heavy oil, emulsion fuel, or nanoemulsion fuel, and the amount of exhaust gas is reduced.

(Example 1) which showed the flowchart of the method of manufacturing a liquid fuel.

The “liquid fuel” of the present invention refers to a liquid fuel in which heavy oil, water and cyclodextrin are mixed and liquefied in a suspended state.
Here, “mixed” means that heavy oil, water and cyclodextrin are mixed together, and “suspension” means that they are in a liquid state in a suspended state.

  The “heavy oil” contained in the “liquid fuel” of the present invention may be any conventionally known oil, such as A heavy oil or C heavy oil.

The “cyclodextrin” contained in the “liquid fuel” of the present invention may be any conventionally known CD as long as it is useful for improving combustion efficiency and reducing exhaust gas. -Β-cyclodextrin (hereinafter sometimes simply referred to as HP-β-CD), hydroxypropyl-α-cyclodextrin (hereinafter sometimes simply referred to as HP-α-CD), hydroxypropyl-γ-cyclo Examples include dextrin (hereinafter sometimes simply referred to as HP-γ-CD) or β-cyclodextrin (hereinafter sometimes simply referred to as β-CD). These CDs may be used alone or in combination of two or more, and may be included in the “liquid fuel” of the present invention, or may be combined with other useful CDs.
This CD may be prepared independently or commercially available. Examples of commercially available products include CAVASOL (registered trademark) W7 HP, CAVASOL (registered trademark) W7 HP TL, CAVASOL (registered trademark) W6 HP, CAVASOL (registered trademark) W6 HP TL, CAVASOL (registered trademark) W8 HP or And CAVAMAX (registered trademark) W7 (both manufactured by Wacker).

In producing the “liquid fuel” of the present invention, the “cyclodextrin” may be used in the form of a powder, or may be used as a solution of cyclodextrin dissolved in water or the like. The cyclodextrin solution may be neutral or alkaline, and sodium hydroxide or the like may be added together to make it alkaline.
In obtaining the “liquid fuel” of the present invention, “cyclodextrin” is preferably added at 0.005 w / w% to 5.0 w / w% with respect to the liquid fuel. In particular, it is preferably added at 0.01 w / w% to 2.0 w / w%, and more preferably 0.01 w / w% to 0.5 w / w%.

In obtaining the “liquid fuel” of the present invention, “water” is pond water, river water, ground water, industrial water, etc., which is purified, ion-exchanged water such as tap water, NaOH ion-exchange aqueous solution, etc. Etc. are preferably used.
“Water” is preferably added at 1.0 v / v% to 50.0 v / v%, particularly 5.0 v / v% to 10.0 v / v% with respect to the liquid fuel. Is preferred.

In order to obtain the liquid fuel of the present invention, the “method for producing a liquid fuel” of the present invention is a method including “a step of allowing a mixture of heavy oil, water and cyclodextrin to pass through a minute gap under pressure”. It may include other useful methods.
Examples of the “step of passing a mixture of heavy oil, water and cyclodextrin under pressure through a fine gap” include a step of dispersing the mixture of heavy oil, water and CD using a high-speed rotating machine. . This step is preferably performed using a plasma nanomachine.

The plasma nanomachine refers to a machine that causes nanomolecules by causing molecular fluctuations in materials necessary for producing liquid fuels such as heavy oil and water by rotating a brush rotor at high speed. In the production of the liquid fuel of the present invention, any conventionally known plasma nanomachine can be used, but after adding heavy oil, water, etc., energization and discharge in liquid enhance the molecular kinetic energy. Thus, it is preferable to dissociate water molecules and to decompose a part of heavy oil.
An apparatus developed by the present inventors can also be used as such a plasma nanomachine. One of the plasma nanomachines developed by the present inventors is a plasma nanomachine having the following characteristics. These voltages, the number of rotor rotations at the + electrode, the number of electrodes, the number of electrodes at the − electrode, and the like can be changed according to the processing capability of the plasma nanomachine.
Voltage: 220V (three-layer AC)
+ Electrode Rotor rotation speed: 3600 rpm, number of electrodes (number of terminals): 1200
-Electrode fixation, number of electrodes (number of terminals): 300
Terminal clearance: 2mm

The “liquid fuel production method” of the present invention may further include a step of dispersing using a micro-nano machine. When the step of dispersing using a micro / nano machine is performed in a state where CD is mixed, the particles of heavy oil and water can be further refined.
A micro-nano machine refers to an apparatus intended to homogenize nano-sized molecules and increase the dissolved oxygen content (DO value) in a liquid. In the production of the liquid fuel of the present invention, any conventionally known micro / nano machine can be used, and as such a micro / nano machine, an apparatus developed by the present inventors can be used. Moreover, the mixing apparatus made from Nikuni Co., Ltd. which generate | occur | produces a micro nano bubble can also be used. One of the micro-nano machines developed by the present inventors is a micro-nano machine having the following characteristics. These nanonized circulation amount, nanonization circulation pressure, AIR supply amount, and the like can be changed according to the processing capability of the micro-nano machine.
Nanonized circulation: 4000L / Hr
Nano-circulation pressure: 0.4 MPa
AIR supply amount: 5 L / min

The “heavy oil and / or water nano-accelerator” of the present invention refers to particles of heavy oil and water used as raw materials in the production of liquid fuel with high combustion efficiency and reduced exhaust gas amount as in the present invention. An agent for promoting miniaturization.
The “nanoization accelerator” of the present invention may be any conventionally known CD as long as it is a useful CD in the production of such a liquid fuel. As such CD, for example, HP- Any one or more of β-CD, HP-α-CD, HP-γ-CD and β-CD can be mentioned. In addition, any one or more of HP-β-CD, HP-α-CD, HP-γ-CD, and β-CD can be used in combination with one or more of other useful CDs. It may be included in the “accelerator”.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these.

[Example 1]
1. Preparation of Nanoization Accelerator Hydroxypropyl-β-cyclodextrin (HP-β-CD) (Cavasol® W7 HP) was used as the nanoization promoter.

2. Method for Producing Liquid Fuel A method for producing a liquid fuel will be described with reference to FIG. FIG. 1 is a diagram showing a process diagram (next steps 1 to 5) for manufacturing a liquid fuel.

Step 1: Step of adding a nano-promoting agent containing heavy oil, water and CD to the plasma nanomachine Step 2: After passing through Step 1, the plasma nanomachine is energized to nanoscale heavy oil and / or water, and heavy oil Step 3 to generate a reaction product of water and water Step 2: After Step 2, nano-sized heavy oil and / or water, Step of adding these reactants to the micro-nano machine Step 4: After Step 3, Passing through the nano-machine, adding air, nano-ized heavy oil and / or water, and making these reactants more uniform nano-compounds and dissolving oxygen in the air Step 5: Step 4 After that, the obtained liquid fuel is circulated through the micro-nano machine to make it into a uniform nano-compound and dissolve oxygen in the air.

[Example 2]
A liquid fuel obtained by the method for producing a liquid fuel shown in Example 1, using 92 L of heavy oil A as heavy oil, adding 8 w of water and 0.01 w / w% of HP-β-CD as a nano-promoting agent. The combustion efficiency was investigated. As a comparison, the combustion efficiency of a fuel of a comparative example obtained by adding only 100 A of heavy oil A or 92 L of heavy oil A and 8 L of water was also examined.
Combustion efficiencies using these liquid fuels and the like are shown in Table 1 as the results (average value of 10 times or more) of operating a 1-t once-through boiler (model: Z-1000, manufactured by Miura Kogyo Co., Ltd.) for 17 hours.

In the production of the liquid fuel and the fuel of the comparative example, the plasma nano machine and the micro nano machine were energized under the following conditions. These setting conditions can be changed except for terminal clearance, and the conditions can be changed appropriately according to the type, amount, etc. of heavy oil, water, and nano-promoter used in the production of liquid fuel. is there.
1. Plasma nano machine Voltage: 220V (Three-layer AC)
+ Electrode Rotor rotation speed: 3600 rpm, number of electrodes (number of terminals): 1200
-Electrode fixation, number of electrodes (number of terminals): 300
Terminal clearance: 2mm
2. Micro-nano machine Nano-circulation amount: 4000L / Hr
Nano-circulation pressure: 0.4 MPa
AIR supply amount: 5 L / min

The separation in Table 1 means that the liquid fuel of the present invention and the fuel of the comparative example (A heavy oil + water nano-form) have higher specific gravity than the non-nano-form (A heavy oil alone) and are separated into the lower layer. The separation time is shown. The uniform stability of each fuel was evaluated from this separation time. As a result, it was confirmed that the liquid fuel of the present invention was improved in dissolution uniformity due to the slow separation time due to the addition of the nano-izing accelerator.
In addition, the fluidity in Table 1 means the moment of the liquid fuel of the present invention supplied to the boiler under a certain condition, the fuel of the comparative example (A heavy oil + water nano-compound) or the non-nano-form (A heavy oil alone). This is a value obtained by measuring the flow velocity. As shown in Table 1, it was confirmed that the liquid fuel of the present invention showed a viscosity similar to that of A heavy oil.
Furthermore, the evaporation factor in Table 1 indicates a multiple of the amount of water evaporated with the fuel used under certain conditions. As shown in Table 1, the liquid fuel of the present invention has a higher evaporation factor than the comparative fuel (A heavy oil + water nano-form) or non-nano-form (A heavy oil alone), conventional emulsion fuel, etc. It was confirmed that this was a liquid fuel with improved combustion efficiency.

Example 3
Example 1 Using 92 L of A heavy oil as heavy oil, adding 8 L of water and 0.01 w / w%, 0.05 w / w% or 0.1 w / w% of HP-β-CD as a nano-promoting agent The combustion efficiency of the liquid fuel obtained by the liquid fuel production method shown in Fig. 1 was investigated.
As a comparison, the combustion efficiency of the fuel of a comparative example obtained by adding only A heavy oil (100 L) or only 92 L of A heavy oil and 8 L of water without adding the nano-izing accelerator was also examined.
Moreover, methyl-β-cyclodextrin (M-β-CD) (Cavasol (registered trademark) W7 M) (hereinafter simply referred to as M-β-CD) may be used as a candidate for cyclodextrin serving as a nano-promoter. ) Or α-cyclodextrin (α-CD) (CAVAMAX (registered trademark) W6 FOOD) (hereinafter may be simply referred to as α-CD), respectively, is also produced and burned. The efficiency was examined.
Combustion efficiencies using these liquid fuels and the like are shown in Table 2 as results (average value of 10 times or more) of operating a 1 t once-through boiler (model: Z-1000, manufactured by Miura Kogyo Co., Ltd.) for 17 hours.
Note that the plasma nanomachine and the micronano machine used in the production of the liquid fuel of the present invention and the fuel of the comparative example were the same as those in Example 2.

  As shown in Table 2, the liquid fuel of the present invention is a heavy oil A in any of the additions of 0.01 w / w%, 0.05 w / w%, or 0.1 w / w% of the nano-accelerator. It was confirmed that the fuel was a liquid fuel having a higher evaporation factor and improved combustion efficiency compared to the fuel of the comparative example. From this result, it was confirmed that the combustion efficiency was remarkably improved when HP-β-CD was used as the nano-ized accelerator.

Example 4
Liquid fuel A to C is operated by operating the plasma nano machine and the micro nano machine under conditions A to C described in Table 3 using A heavy oil as the heavy oil and HP-β-CD as the nano-accelerator. Manufactured.
Regarding the obtained liquid fuel, the combustion efficiency when a 2t once-through boiler (manufactured by IHI Co., Ltd.) was operated for 4 hours, 8 hours, 12 hours, or 16 hours and evaluated by the evaporation multiple value is shown in Table 4. It was. For comparison, the combustion efficiency of only A heavy oil was also examined.

  As shown in Table 4, all of the liquid fuels of the present invention showed higher combustion efficiency than heavy fuel oil A when the operation time was 4 hours. In particular, the liquid fuel produced under the condition C was a preferable liquid fuel because it stably maintained high combustion efficiency even when the operation time was 16 hours.

Example 5
The effect given to the liquid fuel produced by the liquid fuel production method of the present invention was confirmed by the following test.
I. Confirmation of water dispersibility Water and oil, which are raw materials for liquid fuel, are energized while mixing and stirring, and using a particle size distribution measuring device (SALD-300V Model-2, manufactured by Shimadzu Corporation) By measuring the particle size distribution and recording the change, the water dispersibility in the produced liquid fuel was confirmed.

<Test 1>
1. Sample Isooctane (2,2,4-trimethylpentane) (manufactured by Wako Pure Chemical Industries, Ltd.), tap water, and HP-β-CD as a nano-promoting agent were used as test oils and fats instead of heavy oil. Further, sodium hydroxide (granular) (manufactured by Wako Pure Chemical Industries, Ltd.) was used.

2. Method for measuring water dispersibility << Pattern 1 >>
Into a 1 L graduated cylinder, 500 mL of tap water and 500 mL of isooctane were placed, and a current of 16 V and 0.060 A was passed through a small electrode while stirring with a magnetic stirrer.
25 mL of an oil layer sample was taken out before the start of energization (0 seconds), 12 seconds, 72 seconds and 10 minutes after the start of energization, and the change in particle size was recorded by a particle size distribution measuring device.
<< Pattern 2 >>
500 mL of tap water was put in a 1 L graduated cylinder, and 1.07 g of HP-β-CD was dissolved. To this, 500 mL of isooctane was added, and a current of 16 V and 0.060 A was passed through a small electrode while stirring with a magnetic stirrer.
25 mL of an oil layer sample was taken out before the start of energization (0 seconds), 12 seconds, 72 seconds and 10 minutes after the start of energization, and the change in particle size was recorded by a particle size distribution measuring device.
<< Pattern 3 >>
500 mL of tap water was put in a 1 L graduated cylinder to dissolve 1.07 g of HP-β-CD and 1.12 g of sodium hydroxide. To this, 500 mL of isooctane was added, and a current of 11 to 13 V and 2.50 A was passed through a small electrode while stirring with a magnetic stirrer.
25 mL of an oil layer sample was taken out before the start of energization (0 seconds), 12 seconds, 72 seconds and 10 minutes after the start of energization, and the change in particle size was recorded by a particle size distribution measuring device.

3. Results Table 5 shows the results of changes in the particle size distribution obtained by the energization treatment obtained in each of the measurement methods of Patterns 1 to 3.
As shown in Table 5, the particle diameter of water droplets generated in the oil was not stable under the conditions of Pattern 1 in which HP-β-CD was not added as a nano-promoting agent. On the other hand, in patterns 2 and 3 to which HP-β-CD was added, it was confirmed that the particle diameter of the water droplet gradually decreased with the energization time.

<Test 2>
1) Sample As test fats and oils, isooctane (2,2,4-trimethylpentane) (manufactured by Wako Pure Chemical Industries, Ltd.) and NaOH ion exchange aqueous solution were used as samples. Moreover, HP-β-CD, M-β-CD, or α-CD was used as a sample as a nano-accelerator candidate. For comparison, glycerin fatty acid ester (Wako Pure Chemical Industries, Ltd.) was used.

2) Method for measuring water dispersibility (1) Cyclodextrin aqueous solution (pH 12.1: 0.01M, NaOH) in which HP-β-CD, M-β-CD or α-CD is dissolved as a candidate for nano-promoting agent An ion exchange aqueous solution) was prepared. For comparison, an aqueous surfactant solution in which glycerin fatty acid ester was dissolved was also prepared.
(2) 400 mL of a CD aqueous solution (pH 12.1: 0.01 M, NaOH ion exchange aqueous solution), a surfactant aqueous solution or a NaOH ion exchange aqueous solution (negative control) prepared in (1) above in a 1 L sized cylinder. 400 mL of isooctane was added.
The concentration of the nano-promoting agent contained in the total 800 mL of the mixed solution was adjusted to 0.1 w / v% when HP-β-CD was used as the nano-promoting agent. When M-β-CD or α-CD was used, the molar concentration was adjusted to match that when HP-β-CD was used. Moreover, it prepared so that glycerin fatty acid ester might be 0.1 w / v%.
(3) The small graduated cylinder electrode of (2) above was submerged, a magnetic stirrer was added, and the mixture was stirred for 5 minutes. After 5 minutes, 25 mL of the oil layer sample was taken out and used as the sample before the start of energization (0 minute). Energization (18V) of the graduated cylinder was started, and 25 mL of an oil layer sample was taken out for 1 minute, 5 minutes, 10 minutes, 20 minutes, and 30 minutes after the start of electricity supply.
(4) About each sample extract | collected in said (3), the change of a particle diameter was recorded with the particle diameter distribution measuring apparatus.
In the case of using HP-β-CD as the nano-promoting agent, the change in particle diameter was also recorded for a sample obtained only by stirring without conducting electricity as a comparison.

3) Results Table 6 shows the results of changes in the particle size distribution due to the energization treatment obtained in the measurement method of 2) above.
As shown in Table 6, it was confirmed that when HP-β-CD was added as a nano-promoting agent, the particle size of the water droplets became smaller and smaller especially with the energization time.

  According to the present invention, it is possible to provide a liquid fuel that exhibits a special effect that combustion efficiency is higher than that of conventional petrochemical fuel, emulsion fuel, or nanoemulsion fuel and the amount of exhaust gas is reduced.

Claims (7)

Liquid fuel in which heavy oil, water and cyclodextrin are mixed and suspended. The liquid fuel according to claim 1, wherein the heavy oil is one or more of A heavy oil and C heavy oil. The cyclodextrin is hydroxypropyl-β-cyclodextrin (HP-β-CD), hydroxypropyl-α-cyclodextrin (HP-α-CD), hydroxypropyl-γ-cyclodextrin (HP-γ-CD) or β The liquid fuel according to claim 1 or 2, which is at least one of cyclodextrin (β-CD). The liquid fuel according to any one of claims 1 to 3, wherein the cyclodextrin is added at 0.005 w / w% to 5.0 w / w%. The liquid fuel according to claim 1, wherein the water is added at 1.0 v / v% to 50.0 v / v%. The manufacturing method of the liquid fuel in any one of Claims 1-5 including the process of pressurizing and passing the mixture of heavy oil, water, and cyclodextrin through a fine gap. Hydroxypropyl-β-cyclodextrin (HP-β-CD), hydroxypropyl-α-cyclodextrin (HP-α-CD), hydroxypropyl-γ-cyclodextrin (HP-γ-CD) or β-cyclodextrin ( A fuel oil and / or water nano-promoter containing any one or more of (β-CD).

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