JP2011140551A - Liquid fuel, method for manufacturing the same and oxidizer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently manufacturing a glycerol-free liquid fuel using glycerol-containing industrial waste produced as a byproduct at manufacturing of e.g. a biodiesel fuel, and an oxidizer composition used in the manufacturing method. <P>SOLUTION: The method for manufacturing a liquid fuel includes a mixing step of mixing the glycerol-containing industrial waste, a mineral oil such as kerosene and the oxidizer composition comprising an oxidizer such as hydrogen peroxide and an acid. Preferably, in the mixing step, after mixing the industrial waste and the mineral oil, the resulting mixture is further mixed with the oxidizer composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a liquid fuel, a method for producing the same, and an oxidant composition. More specifically, for example, a method for producing a liquid fuel using a glycerin-containing component by-produced as a production raw material during production of biodiesel fuel, Moreover, it is related with the oxidizing agent composition used for the manufacture. This liquid fuel is suitable as a fuel substitute for heavy oil.

  In recent years, biodiesel fuel suitable as a light oil alternative fuel has been manufactured using natural fats and oils such as vegetable oils and animal fats, or waste cooking oils discarded from food factories and households. However, a by-product with a high ratio of glycerin is obtained during the production of biodiesel fuel, and its utilization method is a problem. The reason is that in addition to glycerin, this by-product contains impurities derived from vegetable oils, fats / fatty acids, catalysts, etc., and incineration is often not easy. And in order to extract glycerol from a by-product and to utilize effectively, it is said that sufficient refinement | purification processing is required.

On the other hand, a method for reforming the by-product to produce another fuel, for example, a heavy oil substitute fuel, has been studied.
For example, Patent Document 1 discloses a method for producing a fatty acid alkyl ester using a strong alkali catalyst as a reaction catalyst for fats and oils and an aliphatic alcohol. In this production method, water and alcohol are added to a heavy liquid part containing glycerin as a main component to obtain a preparation solution, and an inorganic acid is added to the preparation solution so that the pH is 3.0 to 7.0. Then, the inorganic salt is removed, and then water and alcohol are removed by the first distillation. Thereafter, the distillate obtained by the second distillation is further phase-separated into purified glycerin and purified fatty acid alkyl ester. And the distillation remainder is used as heavy oil alternative fuel.
In Patent Document 2, a reaction liquid containing an alkyl ester of fatty acid, glycerin and a calcium-based solid catalyst is produced by reacting fats and oils with an aliphatic alcohol in the presence of a solid catalyst made of calcium oxide or the like. A step of separating the reaction liquid into a light liquid part mainly composed of an alkyl ester of a fatty acid and a heavy liquid part composed of a mixture of glycerin and a calcium-based solid catalyst, and using the separated heavy liquid part as fuel. A method for producing a fatty acid alkyl ester is disclosed.

JP 2005-60587 A JP 2008-143983 A

  As mentioned above, the by-product obtained during the production of biodiesel fuel is a mixture of various substances. And since the properties are usually highly viscous liquids or solids, workability may be reduced during handling. Therefore, there are cases where it is difficult to apply the multi-step and complicated processes described in Patent Documents 1 and 2 as they are.

  The present invention uses a glycerin-containing component (hereinafter referred to as “glycerin-containing industrial waste”) typified by a by-product obtained during the production of biodiesel fuel as a production raw material, and does not contain glycerin. Is to provide a method for producing the oxidant simply and efficiently, and an oxidant composition used for the production.

The present invention is shown below.
1. The manufacturing method of the liquid fuel characterized by including the mixing process which mixes the industrial waste containing glycerol, mineral oil, and the oxidizing agent composition containing an oxidizing agent and an acid.
2. 2. The method for producing a liquid fuel as described in 1 above, wherein in the mixing step, the industrial waste and the mineral oil are mixed, and then the mixture and the oxidant composition are further mixed.
3. 3. The method for producing a liquid fuel as described in 1 or 2 above, wherein the oxidizing agent contains hydrogen peroxide.
4). 4. The method for producing a liquid fuel as described in any one of 1 to 3 above, wherein the acid contains acetic acid.
5. 5. The method for producing a liquid fuel as described in any one of 1 to 4 above, wherein the mineral oil is at least one selected from kerosene and heavy oil.
6). The mixing ratio of the industrial waste and the mineral oil is 1 to 99% by mass and 1 to 99% by mass, respectively, when the total of both is 100% by mass, respectively. Method for producing liquid fuel.
7). A liquid fuel produced by the method according to any one of 1 to 6 above.
8). 7. An oxidizer composition used in the method according to any one of 1 to 6 above, comprising an oxidizer and an acid.
9. 9. The oxidant composition according to 8 above, wherein the oxidant is hydrogen peroxide and the acid is acetic acid.

According to the method for producing a liquid fuel of the present invention, a liquid fuel that does not contain glycerin and contains most of the used mineral oil can be easily and efficiently produced.
When the oxidizing agent contains hydrogen peroxide, it is possible to improve the liquid fuel conversion rate of industrial waste.
When the mineral oil is at least one selected from kerosene and heavy oil, not only can the industrial waste be processed appropriately, but also the liquid fuel obtained can contain kerosene, This can be used as it is.

  According to the oxidizing agent composition of the present invention, liquid fuel is used for industrial waste containing glycerin, preferably industrial waste containing glycerin, which is a by-product obtained during the production of biodiesel fuel. Can be manufactured efficiently.

  The manufacturing method of the liquid fuel of this invention is equipped with the mixing process which mixes the industrial waste (glycerin containing industrial waste) containing glycerol, mineral oil, and the oxidizing agent composition containing an oxidizing agent and an acid.

  The glycerin-containing industrial waste is not particularly limited as long as it is a by-product, a residue, or the like from a factory or household and contains glycerin. The content of glycerin contained in the glycerin-containing industrial waste is preferably 10 to 100% by mass, more preferably 20 to 90% by mass, and still more preferably, when the entire glycerin-containing industrial waste is 100% by mass. Is 30 to 80% by mass. The other components contained in the glycerin-containing industrial waste are not particularly limited. For example, by-products generated during the production of biodiesel fuel are usually impurities, fats and oils derived from protein, starch, vegetable oil, etc. Fatty acids (hereinafter referred to as “organic impurities”); catalyst residues; alcohols such as methanol are included. In the present invention, as a glycerin-containing industrial waste, it is preferable to use a by-product generated during the production of biodiesel fuel. The content ratio of glycerin and the like contained in the by-product generated during the production of the biodiesel fuel is not specified because it depends on the production conditions of the biodiesel fuel. Usually, glycerin is 10 to 80% by mass, organic Impurities are 15 to 60% by mass, and alcohol is 5 to 30% by mass.

  The glycerin-containing industrial waste is a mixture of various substances as described above, and is usually a highly viscous liquid or solid. In the mixing step according to the present invention, it is preferably used in a liquid state by heating or combined use with other components. The “liquid state” may be a state in which all of the constituent components are in a liquid state, or may be a state in which some of the constituent components are liquefied and other components are dispersed.

  Although the said mineral oil is not specifically limited, Petroleum naphtha, gasoline, heavy oil, kerosene, light oil etc. which are fuel oils can be used. These may be used alone or in combination of two or more. When producing heavy oil substitute fuel according to the present invention, heavy oil and kerosene are preferred, and kerosene is particularly preferred.

  The preferable usage-amount of the said mineral oil is as follows. That is, the ratio of the glycerin-containing industrial waste and the mineral oil is preferably 1 to 99% by mass and 1 to 99% by mass, and more preferably 5 to 95% when the total of both is 100% by mass. They are 10 mass% and 5-95 mass%, More preferably, they are 10-90 mass% and 10-90 mass%. By making the ratio of the usage-amount of the said glycerin containing industrial waste and the said mineral oil into the said range, the mixing process which concerns on this invention can be advanced smoothly.

  Moreover, the said oxidizing agent composition is a composition containing an oxidizing agent and an acid. The present inventors presume that this composition has an action of oxidizing and decomposing organic impurities contained in glycerin-containing industrial waste. And in a mixing process, it is estimated that reaction of a decomposition product and glycerol advances.

The oxidizing agent is not particularly limited as long as it is not a compound that loses the above action by contact with the mineral oil, the acid contained in the oxidizing agent composition, and water.
Examples of the oxidizing agent include hydrogen peroxide, calcium peroxide, potassium permanganate, potassium chlorate, sodium bromate, potassium bromate, sodium hypochlorite, calcium hypochlorite, chloramine, peracetic acid, perbenzoic acid. Acid, metachloroperbenzoic acid, monoperoxyphthalic acid, performic acid, N-chlorosuccinimide, N-bromosuccinimide, and the like. These may be used alone or in combination of two or more. In the present invention, hydrogen peroxide is preferred.

  Moreover, as said acid, any of an inorganic acid and an organic acid may be used, and you may use together. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid and the like. Examples of the organic acid include acetic acid, formic acid, propionic acid, and citric acid. In the present invention, acetic acid is preferred.

  The content ratio of the oxidant and the acid contained in the oxidant composition is preferably 1 to 30% by volume and 70 to 99% by volume, more preferably, when the total of both is 100% by volume. 3 to 20 vol% and 80 to 97 vol%, more preferably 5 to 12 vol% and 88 to 95 vol%. If it is the said ratio, the oxidative decomposition of an organic impurity can be advanced smoothly.

  The oxidant composition usually contains water in addition to the oxidant and acid. The water content is preferably 20 to 80% by volume, more preferably 35 to 60% by volume, based on the entire oxidant composition.

The amount of the oxidant composition used is preferably 1 to 10 parts by mass, more preferably 2 to 2 parts when the total amount of the glycerin-containing industrial waste, mineral oil and oxidant composition is 100 parts by mass. 8 parts by mass, more preferably 2.5 to 5 parts by mass.
The amount of the oxidizing agent used is preferably 0.04 to 1.5 parts by mass, more preferably 0.1 to 1.0 parts by mass, when the amount of the glycerin-containing industrial waste used is 100 parts by mass. More preferably, it is 0.2 to 0.5 parts by mass.

  In the mixing step, the order of mixing the glycerin-containing industrial waste, the mineral oil, and the oxidizer composition, which are manufacturing raw materials, is not particularly limited. Specific methods include a method of mixing all three types of manufacturing raw materials at once, a method of mixing two types of manufacturing raw materials, and then mixing with the remaining manufacturing raw materials. In the present invention, from the viewpoint of reaction efficiency, after mixing the glycerin-containing industrial waste and mineral oil, the mixture (hereinafter referred to as “first mixture”) and the oxidant composition are further mixed. It is preferable. This preferred method will be described in further detail.

The manufacturing method of the said 1st mixture is not specifically limited, What is necessary is just to mix a glycerin containing industrial waste and mineral oil by a conventionally well-known method, for example, the method using a stirrer.
As a specific method of mixing the glycerin-containing industrial waste and mineral oil, a method of mixing and stirring both together, a method of gradually adding the other while stirring the whole amount of one, both under stirring Examples of the method include mixing while gradually adding.
The glycerin-containing industrial waste and mineral oil are not necessarily compatible with each other, and phase separation may occur when the mixture is left untreated. In the present invention, since a uniform first mixture is obtained, it is preferable to perform mixing with heating. In particular, since the glycerin-containing industrial waste is a highly viscous liquid or solid, (i) a method in which stirring is further continued while heating the glycerin-containing industrial waste and mineral oil at room temperature, (Ii) It is preferable to adopt a method of stirring glycerol-containing industrial waste and mineral oil while heating. The heating temperature in these cases is preferably 50 ° C to 110 ° C, more preferably 60 ° C to 100 ° C, and still more preferably 70 ° C to 90 ° C.
The “uniform first mixture” is meant to include a mixture in which fine bodies of glycerin-containing industrial waste are dispersed in mineral oil.

Then, although a 1st mixture and an oxidizing agent composition are mixed, these mixing methods are not specifically limited. That is, a method of mixing and stirring both together, a method of gradually adding the other while stirring one whole amount, a method of adding one to the other without stirring, and the like.
When the first mixture and the oxidant composition are brought into contact with each other, bubbles are generated from the mixed solution regardless of the presence or absence of stirring, and thus some reaction seems to have occurred. That is, it is considered that the reaction of the first mixture and the oxidant composition has started. In this case, although the generation of bubbles gradually subsides, from the viewpoint of workability, when the mixing of the first mixture and the oxidant composition is started, the oxidant composition is added to the first mixture that is not in the stirring state. Is preferably added. Even if only the oxidant composition is added, both are sufficiently mixed. And after generation | occurrence | production of a bubble calms down, you may stir as needed.
In addition, when the first mixture is manufactured while being heated as described above, it may be mixed with the oxidant composition in the heated state, and after the heating is stopped, the temperature is changed from room temperature to the heating temperature. You may mix the 1st mixture of the temperature of between, and an oxidizing agent composition.

A mixture of manufacturing raw materials is not obtained by the mixing step. As described above, it is estimated that a reaction occurs between the glycerin-containing industrial waste and the oxidant composition, and this is called a reaction mixture.
This reaction mixture is usually a mixture composed of a phase mainly containing a conversion product from glycerin and mineral oil, and a phase mainly containing components that cannot be liquid fuel (usually in a tar form). . And by leaving still for a while, these isolate | separate into an upper phase and a lower phase, respectively. By extracting the upper phase, the liquid fuel according to the present invention can be obtained.

Note that the liquid fuel contained in the upper phase may contain impurities, moisture, and the like. Therefore, in order to make the liquid fuel more pure, the following steps can be further provided. In addition, when the pH of a reaction mixture is not neutral, the neutralization process using an acid or an alkali can be provided before the following processes.
(1) An adsorption step in which an adsorbent is mixed with the reaction mixture to adsorb impurities, (2) a separation step in which the reaction mixture is centrifuged, and an upper phase is recovered. (3) From the upper phase obtained in the separation step, Moisture removal process to remove moisture

  In the present invention, a method in which the adsorption process, the separation process, and the water removal process are sequentially performed, or a method in which the adsorption process is omitted and the separation process and the water removal process are sequentially performed is preferable.

The adsorption process is a component that cannot be a liquid fuel, and adsorbs impurities originally contained in industrial waste containing glycerin, impurities newly generated by the mixing process, impurities introduced from the outside, etc. It is a process to do.
The adsorbent is not particularly limited as long as it does not react with the organic solvent contained in the reaction mixture, and examples thereof include zeolite (crystalline aluminosilicate), alumina, silica alumina (amorphous silica / alumina), and the like. . Of these, zeolite is preferred.
When using the adsorbent, a baking treatment may be performed in advance. In that case, the firing temperature may be 200 ° C. to 500 ° C. or the like.

  The amount of the adsorbent used is usually appropriately selected depending on the amount of the reaction mixture. A preferable usage-amount is 1-10 mass parts with respect to 100 mass parts of reaction mixtures, More preferably, it is 1.5-8 mass parts, More preferably, it is 2-5 mass parts. When the amount of the adsorbent used is within the above range, the removal of impurities can be promoted efficiently.

  In the adsorption step, a method of mixing an adsorbent with the reaction mixture and stirring it is applied. The stirrer to be used is not particularly limited, and a known stirrer or the like can be used. In the stirring, the reaction mixture may or may not be heated.

  As described above, the separation step is a step of centrifuging the reaction mixture containing no adsorbent or the reaction mixture containing the adsorbent. The centrifuge to be used is not particularly limited, and a known centrifuge such as a separation plate centrifuge, a cylindrical centrifuge, a decanter centrifuge, or the like can be used. Centrifugation may be performed while heating the reaction mixture, or may be performed without heating. The rotation speed and separation time are appropriately selected depending on the amount of the reaction mixture.

In the separation step, the upper phase (supernatant liquid) is recovered after centrifugation. Most of this supernatant liquid is liquid fuel and is usually transparent. On the other hand, the lower phase is a tar-like precipitate and is discarded. In addition, when an adsorption process is performed, a precipitate containing an adsorbent is obtained by this separation process.
In the present invention, as described above, only the separation step may be performed, or the adsorption step and the separation step may be performed in this order.

  The water removal step is a step of removing water contained in the supernatant. As described above, the supernatant liquid is mostly liquid fuel, but in order to further increase its purity, the water present in the emulsion state is removed. The method for removing moisture is not particularly limited, and examples thereof include a method using a filter and a method using a moisture adsorbent. And the moisture removal apparatus in oil using these, etc. can be used.

  When a filter is used, the material can be a metal, an alloy, a resin, or the like. In particular, it is preferable to use a stainless steel filter having a pore diameter of 20 to 40 μm, because water stays in the mesh portion due to surface tension and only liquid fuel can be passed.

  Moreover, when using a water | moisture-content adsorption agent, ion exchange resin, activated carbon, molecular sieves, a silica gel, activated alumina, a calcium chloride, a water absorbing resin etc. are mentioned.

  A high-purity liquid fuel can be obtained by subjecting the supernatant to a water removal step. In addition, when a fine powder is contained in the filtrate obtained by the water removal step, it is preferable to perform filtration using a filter having a pore size of 1 μm or less for the removal.

  By the liquid fuel production method of the present invention, most of the used mineral oil is contained in the liquid fuel. Further, all of the glycerin in the glycerin-containing industrial waste is reformed and contained in the liquid fuel. Therefore, the glycerin-containing industrial waste, which has been conventionally discarded as it is, can be made only into tar-like precipitates, and the amount of waste can be reduced. In the mixing step, when kerosene is used as the mineral oil, the obtained liquid fuel can be suitably used as a heavy oil substitute fuel. That is, the physical properties of the liquid fuel have values close to those of heavy oil type 1 No. 1.

  In addition, the oxidant composition of the present invention is a composition containing an oxidant and an acid as described above, and efficiently produces liquid fuel by using it in combination with glycerin-containing industrial waste and mineral oil. can do. In particular, the effect is particularly excellent when the oxidizing agent is hydrogen peroxide and the acid is acetic acid.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist of the present invention. In the following, “parts” and “%” are based on mass unless otherwise specified.

The raw materials used for the production of the liquid fuel are as follows.
(1) Glycerin-containing industrial waste This glycerin-containing industrial waste is recovered as a by-product when a biodiesel fuel is produced by transesterifying waste cooking oil and methanol using an alkali catalyst method. is there. Table 1 shows the composition and physical properties of this glycerin-containing industrial waste.

(2) Mineral oil Kerosene (commercial product) was used.
(3) Oxidizing agent composition A composition obtained by mixing 11.7% hydrogen peroxide solution and 90% aqueous acetic acid solution at a volume ratio of 1: 1 was used.

Example In a stainless steel reaction vessel equipped with stirring means and heating means, 70 parts of glycerin-containing industrial waste and 27 parts of mineral oil were added. And the reaction container was heated, the temperature of the content was 80 degreeC, and it stirred and mixed for 5 minutes.
Thereafter, heating and stirring were stopped, and 3 parts of an oxidant composition was added. Simultaneously with the addition of the oxidant composition, bubbles were generated from the mixed solution, but the generation was completed after about 10 minutes.
Next, 2 parts of zeolite (trade name “Zeofil”, manufactured by Shintohoku Chemical Industry Co., Ltd.) was added to the reaction mixture and stirred.
Thereafter, the mixture is subjected to centrifugal separation (rotation speed: 15,000 rpm) for 2 minutes to perform solid-liquid separation, and the supernatant (upper phase) is recovered, and about 8 parts of precipitate (lower phase) containing the zeolite is collected. ) Was discarded. Then, water is removed from the collected supernatant using a stainless steel filter having a pore diameter of 37 μm, and impurities are removed using a polypropylene filter having a pore diameter of 1 μm, and about 90 parts of a light brown transparent liquid is removed. Obtained.

  The analysis of the liquid obtained as described above was performed by entrusting it to the Physical and Chemical Analysis Center of the Japan Maritime Examination Association. As a result, it was found that the liquid was mainly composed of kerosene and fatty acid methyl ester and contained no glycerin. Moreover, in order to compare with the physical property prescribed | regulated to the Japanese Industrial Standard of heavy oil, it measured about the item shown in Table 2. FIG. The results are shown in Table 2.

  As is apparent from Table 2, the obtained liquid has physical properties equivalent to those of heavy oil type 1 No. 1 in all of flash point, kinematic viscosity, pour point, residual carbon content, moisture, ash content and sulfur content. I understood. Further, the total calorific value was as high as 43.6 MJ, and it was found that it can be used as an excellent liquid fuel.

The liquid fuel obtained by the present invention can be suitably used as boiler, heating furnace, or other fuel oil as a heavy oil substitute fuel.
Moreover, the oxidant composition of the present invention is suitable for the production of the liquid fuel of the present invention.

Claims (9)

  The manufacturing method of the liquid fuel characterized by including the mixing process which mixes the industrial waste containing glycerol, mineral oil, and the oxidizing agent composition containing an oxidizing agent and an acid.   The method for producing a liquid fuel according to claim 1, wherein, in the mixing step, the industrial waste and the mineral oil are mixed, and then the mixture and the oxidant composition are further mixed.   The method for producing a liquid fuel according to claim 1, wherein the oxidizing agent contains hydrogen peroxide.   The method for producing a liquid fuel according to any one of claims 1 to 3, wherein the acid contains acetic acid.   The method for producing a liquid fuel according to any one of claims 1 to 4, wherein the mineral oil is at least one selected from kerosene and heavy oil.   The mixing ratio of the industrial waste and the mineral oil is 1 to 99% by mass and 1 to 99% by mass, respectively, when the total of both is 100% by mass. Liquid fuel production method.   A liquid fuel produced by the method according to claim 1.   An oxidant composition used in the method according to claim 1, comprising an oxidant and an acid.   The oxidant composition according to claim 8, wherein the oxidant is hydrogen peroxide and the acid is acetic acid.