JP5750708B2 - Hydrolyzed fuel and additive-adjusted fuel oil and additive and method for producing them - Google Patents

Description

  The present invention relates to a hydrated fuel, a conditioned fuel oil that can be converted into a hydrated fuel by hydration, an additive to be added thereto, and a production method thereof.

Due to the depletion of petroleum resources and environmental problems associated with the use of oil, water-mixed fuels that contain water and fuel oil are attracting attention. It has been already known that a hydrous fuel has a combustion efficiency equivalent to that obtained when only fuel oil is burned, and various fuels have been proposed.
For example, there are Patent Documents 1 to 4 as techniques related to conventional water-added fuel.

JP 2008-81740 “Method for producing emulsion fuel by mixing water and combustible oil in fine particle state, emulsion fuel production apparatus and emulsion fuel” JP2007-284527 “Heavy oil additive” JP-A-2006-111666 “Emulsion fuel production method, emulsion fuel production apparatus, and emulsion fuel utilization apparatus equipped with the emulsion fuel production apparatus” JP-A-2004-67913 “Method for producing water emulsion fuel”

  However, conventional hydrofuels have problems such as lack of combustion stability, long-term stability such as separation of oil and water, and lack of uniformity of oil and water. There wasn't.

Therefore, the present invention achieves uniform dispersion of oil water to improve combustion efficiency, and an additive that can stabilize the uniform dispersion of oil water for a long period of time, and an additive-adjusted fuel oil and water solution obtained by the addition. It is an object of the present invention to provide a fuel and a manufacturing method thereof.
In particular, it is an object to provide a means that does not require the use of a surfactant.

  In order to solve the above problems, the method for producing an additive of the present invention comprises the following configuration. That is, it is a method for producing an additive used to produce a hydrated fuel or a conditioned fuel oil prior to its addition to a fuel oil, which is relatively free from fatty acids or relatively high molecular weight alcohols. And a step of dissolving an alcohol having a low molecular weight to produce an intermediate product 1 and a step of adding ammonia water or ammonia gas to the intermediate product 1 to produce a desired additive. To do.

  Here, as fuel oil, gasoline, kerosene, light oil, A heavy oil, B heavy oil, C heavy oil, crude vegetable oil, animal oil, waste oil and paper wastewater black liquor can be used.

  Fatty acids include butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, α-linolenic acid, stearidonic acid, eicosapentaene Any of acid, docosahexaenoic acid, linoleic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, oleic acid, maleic acid erucate, fumaric acid, dodecanoic acid, or an ester thereof is suitable.

  As alcohols having a relatively large molecular weight, pentanol, hexanol, pentanol, undecanol, dodecanol, and tridecanol are suitable.

  As the alcohol having a relatively small molecular weight, methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerin or a mixture thereof is preferable.

  The mixing ratio of fatty acids or relatively high molecular weight alcohols, relatively low molecular weight alcohols, ammonia water or ammonia gas is 1: 1.0 to 2.5: 0.001 to 0.7 (mol concentration). ), More preferably 1: 1.1 to 2.2: 0.003 to 0.2 (mol concentration).

  The additive of the present invention is an additive produced by the above-described production method, and includes, as a raw material, at least fatty acids or relatively high molecular weight alcohols, relatively low molecular weight alcohols or mixtures thereof, aqueous ammonia or It has an ammonia gas.

  The method for producing an additive-adjusted fuel oil according to the present invention is a method for producing an adjusted fuel oil prior to addition that can be converted to a water-added fuel by addition of water. It has the step which produces | generates oil, It is characterized by the above-mentioned.

  The mixing ratio of the additive and the fuel oil is preferably 0.03 to 1: 1 (volume), more preferably 0.10 to 0.75: 1 (volume).

  The additive-adjusted fuel oil of the present invention is an additive-adjusted fuel oil produced by the above-described production method, and includes at least fatty acids or relatively high molecular weight alcohols and relatively low molecular weights as raw materials for the additives. It has an alcohol or a mixture thereof, aqueous ammonia or ammonia gas.

  The method for producing a hydrolyzed fuel according to the present invention includes a step of adding water to the additive-adjusted fuel oil to produce a desired hydrolyzed fuel.

  The mixing ratio of water and additive-adjusted fuel oil is preferably 0.1 to 1: 1 (volume), more preferably 0.2 to 0.6: 1 (volume).

  The water fuel of the present invention is a water fuel produced by the above-described production method, and at least as a raw material for the additive, at least fatty acids or relatively high molecular weight alcohols, relatively low molecular weight alcohols or mixtures thereof, It has ammonia water or ammonia gas.

The water-added fuel obtained by the present invention achieves a uniform dispersion of oil and water by adding appropriate additives to improve combustion efficiency, and the uniform dispersion of the oil and water is stable over a long period of time. It can be transported and stored as fuel oil and is highly convenient.
Further, it is not necessary to use a surfactant, and the number of manufacturing steps can be reduced.

Explanatory drawing which shows the flow which produces water fuel Explanatory drawing which shows the Example which manufactures an additive Explanatory drawing which shows the Example which manufactures an additive adjustment fuel oil Explanatory drawing which shows the Example which manufactures water supply fuel Photo of experimental results showing changes in water content with time Photo of experimental results showing the difference depending on the raw material mixing ratio

  Hereinafter, embodiments of the present invention will be described based on examples shown in the drawings. The embodiment is not limited to the following examples, and the design can be changed as appropriate using a conventionally known technique such as the above-mentioned patent document without departing from the gist of the present invention.

The present inventor has obtained the knowledge that a uniform dispersion of oil water in the hydrofuel and a long-term stabilization thereof can be achieved by adding a specific additive to the fuel oil. For the preparation of the fuel for adjusting the fuel and additives and the process for producing them.
Fuel oil generally refers to combustible oils such as gasoline, kerosene, light oil, A heavy oil, B heavy oil, C heavy oil, crude oil, vegetable oil, animal oil, waste oil, and paper mill waste oil (black liquor). And the water-added fuel of this invention mixes the predetermined amount of water and the additive by this invention with the fuel oil.

  As an extension of that research, the present inventor has obtained the knowledge that an additive for a hydrolyzed fuel can be produced without using a surfactant, and has reached the present invention. Compared with Japanese Patent Application No. 2008-270038, it is not necessary to add an amine compound, and this is a method that greatly simplifies the production steps.

FIG. 1 is an explanatory diagram showing a flow of generating water fuel.
The method for producing the additive is as follows.
First, an intermediate product 1 is produced by dissolving relatively small molecular weight alcohols in fatty acids or relatively large molecular weight alcohols.
In addition, fatty acids are good not only as a fatty acid but as a mixture with fatty acid ester.

  Here, alcohols having a relatively large molecular weight are liquids having a large alkyl group, such as pentanol, hexanol, pentanol, undecanol, dodecanol, tridecanol, and the like. Alcohol having a side chain such as an iso compound may be used.

  The alcohol having a relatively small molecular weight is a liquid having a small alkyl group, and refers to, for example, methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerin or a mixture thereof.

  Examples of fatty acids include butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, α-linolenic acid, stearidonic acid , Eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, oleic acid, erucic acid maleic acid, fumaric acid, dodecanoic acid, etc. This refers to those that can be melted into alcohols having a relatively low molecular weight such as ethanol and propanol.

Next, ammonia water or ammonia gas is added to the intermediate product 1, and the mixture is stirred well and adjusted to a certain condition to produce the additive of the present invention.
If the ammonia gas is added excessively, the additive gels, so it is preferable to adjust the amount. When ammonia water is added, it gels because water already exists.
The reaction temperature at the time of production is preferably 30 to 40 ° C., and the stirring conditions are preferably stirring in a range where there is little air contamination. It is preferable to sufficiently stir the reaction so that the reaction becomes uniform because it generates heat during the production.

Since there are various combinations in mixing raw materials, the optimum ratio varies depending on the raw materials, but the following values can be used as a rough guideline.
Fatty acids or relatively high molecular weight alcohols: relatively low molecular weight alcohols or mixtures thereof: ammonia water or ammonia gas = 1: 1.0-2.5: 0.001-0.7 (mol concentration)
More preferably, fatty acids or relatively high molecular weight alcohols: relatively low molecular weight alcohols or mixtures thereof: ammonia water or ammonia gas = 1: 1.1 to 2.2: 0.003 to 0.2 ( mol concentration).

(Example)
Examples of manufacturing the additive are as follows.
As shown in FIG. 2, an additive could be produced by stirring a mixed solution of 3.94 mol of methanol and 0.55 mol of ethylene glycol to 2.50 mol of oleic acid, and sequentially mixing and stirring 0.01 mol of ammonia gas.

The method for adjusting the fuel oil with the additive is as follows.
By mixing and stirring the aforementioned additives according to the present invention in fuel oil such as gasoline, kerosene, light oil, A heavy oil, B heavy oil, C heavy oil, crude oil, vegetable oil, animal oil, waste oil, paper mill waste oil (black liquor), etc. To produce additive-adjusted fuel oil.
You may preserve | save in the state of this additive adjustment fuel oil, and it may add water at the time of use, and may produce | generate a water fuel.

  It is possible to optimize the amount of water to be described later by adjusting the type of the fatty acid as the raw material of the additive as appropriate according to the type of fuel oil to be added.

The required amount of additive varies depending on the type of fuel oil, the type of alcohol with relatively small molecules, and the amount of ammonia gas / ammonia water added, but the following values can be used as rough guidelines.
Additive: Fuel oil = 0.1 to 1: 1 (volume)
More preferably, additive: fuel oil = 0.2 to 0.6: 1 (volume).

(Example)
Examples of producing additive-adjusted fuel oil are as follows.
As shown in FIG. 3, an additive-adjusted fuel oil could be produced by mixing and stirring 5 liters (volume 23%) of additive with 10 liters (volume 77%) of diesel oil.

The adjustment method of the water-added fuel with the additive-adjusted fuel oil is as follows.
Water is mixed with the above-described additive-adjusted fuel oil according to the present invention and stirred to produce a hydrolyzed fuel.
If air is mixed at the time of stirring, there is a risk of generating an explosive air-fuel mixture, so stirring without any air mixing is preferable.

Depending on the ratio of water, the produced fuel liquefies or gels. Moreover, when the ratio of water is too high, the combustion temperature and the calorie calories are reduced. For example, when the fuel is used for a gas turbine, it is preferable that the water is supplied to the boiler.
If the mixing ratio of the raw materials for the additive is not adequate or if the reaction of the additive is not sufficiently accelerated, a white precipitate may be formed after addition depending on the reaction temperature. Is no problem.

As for the amount of water added, the following values can be used as a rough standard as a rough ratio in terms of combustion efficiency and economic efficiency.
Water: Additive-adjusted fuel oil = 0.1-0.8: 1 (volume)
More preferably, water: additive-adjusted fuel oil = 0.2 to 0.6: 1 (volume).

(Example)
The example which manufactured the water fuel is as follows.
As shown in FIG. 4, the water fuel was produced by mixing and stirring 5 liters (volume 28%) of water in 13 liters (volume 72%) of the mixture of light oil and additive.

FIG. 5 is a photograph of the experimental results showing the uniformity of the water fuel.
The ratio of kerosene / additive / water in the produced hydrofuel is kerosene: additive: water = 50%: 25%: 25%, the left is the state after 3 months from the production, the right is the state after 6 months It is.
The hydrated fuel after any lapse of time did not have white turbidity, two-layer separation, or granular separation, and had high transparency and a uniform mixed state of oil and water. This uniform state was stably maintained for a long time.

FIG. 6 is also a photograph of the experimental results showing the uniformity of the water fuel.
On the left side, the ratio of the additive is high, and the ratio of kerosene, additive, and water is
Kerosene: Additive: Water = 50%: 25%: 25%
60%: 20%: 20%,
70%: 15%: 15%,
80%: 10%: 10%,
90%: 5%: 5%,
This is the state after 3 months.
The mixed fuels of any mixing ratio were not cloudy, separated into two layers, or separated into particles, and had high transparency and a uniform mixed state of oil and water. This uniform state was stably maintained for a long time.

  In general, the aspect of the water fuel changes depending on the mixing ratio of oil and water and the adding ratio of additives. However, in the water-added fuel according to the present invention, white turbidity progresses depending on the ratio of water addition and the permeability decreases. However, the oil-water is kept in a uniform mixed state without separation into two layers or granular separation. Further, this uniform state was stably maintained for a long time, and stability was maintained even in an environment of 0 ° C., for example.

As for the use of water fuel, demand is increasing recently as the environmental problem is called out. According to the present invention, the reduction of CO ₂ , NO x, SO x, combustion dust and the like is observed by adding water to the additive-adjusted fuel. In addition, since no ammonium type surfactant or amine compound is used, NOx can be greatly reduced.
It is practical as a fuel for various fuels, such as various types of boilers such as hot air boilers, hot water boilers, steam boilers, and diesel engines for generators, agricultural machinery, automobiles, ships, etc. From the top, the industrial utility value is high.

Claims (9)

A method for producing an additive that is added to a fuel oil and used to produce a transparent hydrated fuel in a uniform mixed state without separation of oil or water, or a conditioned fuel oil before the hydration,
Caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, α-linolenic acid, stearidonic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, γ-linolenic acid, Fatty acids selected from the group of dihomo-γ-linolenic acid, arachidonic acid, oleic acid, erucic acid , dodecanoic acid, alcohols selected from the group of methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerin or Dissolving the mixture to produce intermediate product 1;
Finally, adding aqueous ammonia or ammonia gas to the intermediate product 1 to produce the desired additive,
Fatty acids, alcohols, a mixture ratio of ammonia gas, 1: 1.0~2.5: 0.001~0.7 (mol concentration) and method for producing the additive, characterized by. The method for producing an additive according to claim 1, wherein the fuel oil is any one of gasoline, kerosene, light oil, A heavy oil, B heavy oil, C heavy oil, crude oil, vegetable oil, animal oil, waste oil, and paper wastewater black liquor. An additive produced by the production method according to claim 1 or 2,
As raw materials, at least caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, α-linolenic acid, stearidonic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, γ -Linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, oleic acid, erucic acid , fatty acid selected from the group of dodecanoic acid, selected from the group of methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerin An additive comprising alcohols or a mixture thereof, aqueous ammonia or ammonia gas. A method for producing a conditioned fuel oil prior to hydration that can be hydrated by hydration,
A method for producing an additive-adjusted fuel oil, comprising the step of adding the additive according to claim 3 to the fuel oil to produce a desired additive-adjusted fuel oil. The mixing ratio of additive and fuel oil is
It is 0.03-1: 1 (volume). The manufacturing method of the additive adjustment fuel oil of Claim 4. An additive-adjusted fuel oil produced by the production method according to claim 4 or 5,
As raw materials for additives, at least caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, α-linolenic acid, stearidonic acid, eicosapentaenoic acid, docosahexaenoic acid, linol Fatty acids selected from the group of acids, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, oleic acid, erucic acid , dodecanoic acid, methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerin An additive-adjusted fuel oil comprising an alcohol or a mixture thereof, aqueous ammonia or ammonia gas. A method for producing water-containing fuel,
A method for producing a hydrolyzed fuel, comprising: adding water to the additive-adjusted fuel oil according to claim 6 to produce a desired hydrolyzed fuel. The mixing ratio of water and additive-adjusted fuel oil is
It is 0.1-1: 1 (volume) The manufacturing method of the water-containing fuel of Claim 7. A hydrofuel produced by the production method according to claim 7 or 8,
As raw materials for additives, at least caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, α-linolenic acid, stearidonic acid, eicosapentaenoic acid, docosahexaenoic acid, linol Fatty acids selected from the group of acids, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, oleic acid, erucic acid , dodecanoic acid, methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerin A water-containing fuel characterized by having an alcohol or a mixture thereof, aqueous ammonia or ammonia gas.

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