JP2002206093A - Method for producing fuel for diesel engine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a fuel for Diesel engines from a waste fish oil or a mixture of the waste fish oil with a waste vegetable oil which have been dumped as raw material. SOLUTION: This method for producing the fuel for Diesel engines is characterized by having the primary treatment process comprising subjecting a fish oil (virgin oil or waste fish oil) or a mixture of the fish oil with a vegetable oil (virgin oil or waste vegetable oil) (hereinafter referred to as 'raw material') to an ozone injection treatment and a simultaneous stirring treatment, charging an oxidation-reduction agent and a polymerization inhibitor to the raw material during the stirring treatment, subjecting the raw material to the ozone injection treatment and the stirring treatment, and further charging the oxidation- reduction agent and the polymerization inhibitor during the stirring treatment, the secondary treatment process comprising filtering the product obtained by the primary treatment, again injecting the ozone and simultaneously stirring the product, and further a process comprising charging a vegetable additive to the product obtained by the secondary treatment process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a diesel engine fuel from a substance other than mineral oil such as petroleum, coal or natural gas, and more particularly to a fish oil (virgin oil or fish waste oil) or a mixture of said fish oil and vegetable oil. (Virgin oil or vegetable waste oil).

[0002]

2. Description of the Related Art Naturally, the reserves of fossil fuels or mineral oils, such as oil, coal, or natural gas, which are buried on the earth are limited. It is feared that it will be depleted in decades.

On the other hand, it is said that the amount of fish and the like discarded after being harvested and used for food, feed, fertilizer, etc., ranges from 10 million to 15 million tons in one year in Japan alone. It is estimated that at least ten times more than this is discarded in the world. A part of such fish waste is further mechanically squeezed into solid or powder, and is used as feed for livestock and fertilizers for growing agricultural crops.

[0004] Until a few years ago, most of the effluents generated when squeezing fish wastes were dumped in the ocean. However, this has been a factor in marine pollution, and there has been a growing awareness of the need to protect the global environment. Marine dumping of fish waste is being banned in various countries, and related companies and organizations are currently struggling to dispose of such fish waste.

[0005] After banning the dumping of fish waste into the ocean, there is an example in which the waste liquid squeezed out of fish waste is mixed with heavy oil A and burned for boilers for incineration. It is one of the causes of environmental pollution. In addition, there are many difficult problems that have led to the failure of the boiler kettle.

[0006] The amount of fish waste emissions in Japan is 100
Of the 10,000 to 15 million tons, it is said that 4 to 4.5 million tons of mechanically pressed fish waste oil is discharged annually. When considering environmental pollution on a global level, it is urgent to consider this solution.

[0007] Furthermore, in Japan, the emission amount of vegetable waste oil (waste cooking oil) is publicly announced, about 200,000 tons per year from companies such as the catering industry and food processing factories, and about 200,000 tons from ordinary households, totaling 400,000 tons It is said that.

[0008] Vegetable oil manufacturers ship 1 edible oil.
It is estimated that the amount of vegetable oil is in the range of 100,000 to 1.5 million tons, which indicates that the amount of vegetable oil actually emitted is much higher. Environmental pollution caused by this vegetable waste oil (waste cooking oil) has been highlighted as a social problem, and solutions are urgently needed.

[0009] The types of vegetable waste oil (waste cooking oil) are roughly classified into four types.
There are types. Upper waste oil, middle waste oil, lower waste oil, and sludge. At present, the treatment and disposal methods of vegetable waste oil (waste cooking oil) are as follows. Some of the upper waste oil is reused as feed, soap and food for livestock (it was banned from exporting overseas). A portion of the upper waste oil was used as fuel for diesel engines using methyl esterification technology. Have been. The intermediate waste oil, lower waste oil, and sludge are incinerated by industrial waste intermediate treatment companies using auxiliary fuel. Waste oil from homes is solidified using a solidifying temple agent and is disposed of at municipal incineration plants. In addition, it has been reported as an environmental pollution issue in newspapers etc. by illegal dumping by other vicious companies. In some cases, household waste oil is being flushed from the kitchen sink.

Although there is no real solution to this problem as environmental improvement is called out on a global level, each company, each government, and each local government are currently struggling, but environmental problems that need to be resolved immediately It is.

In recent years, part of vegetable waste oil has been recycled as a fuel for diesel engines by the so-called “methyl esterification technology”. In this technology, first, methanol or ethanol is added to vegetable waste oil (upper waste oil) in an amount of about 30% by weight of the raw material, and subsequently, sodium hydroxide is used as a catalyst in an amount of 1% to 1. Mix 5% and stir. After standing for a while, it is separated into impurities (impurities, water, free fatty acids) with a specific gravity difference, and the upper oil portion is taken out.

[0012] By adding sodium hydroxide to the portion of the oil taken out, transesterification is carried out to form an ester layer and waste glycerin. The portion of the ester layer is refined to be a methyl esterified fuel, while the portion of waste glycerin is neutralized and decomposed by-products and disposed of by an industrial waste trader for a fee.

However, this methyl esterified fuel technology has the following problems. 1. Production cost is high because 30% to 50% of alcohol (methanol or ethanol) is added to the raw material (vegetable waste oil). 2. Plant construction costs are high due to disaster prevention because a large amount of alcohol is used. 3. There is a problem with work safety. 4. Poor yield after purification. Also, only the upper waste oil can be refined among the waste oils. 5. When alcohol and sodium hydroxide are used, if used as fuel, formaldehyde,
Acrolein, benzene, etc. are not clean fuels because they emit more than when diesel is used. 6. Since alcohol is used, trouble easily occurs inside the piston, piston ring, and head inside the diesel engine. 7. Medium waste oil, lower waste oil and sludge cannot be refined, so they are not useful for environmental improvement.

Therefore, the inventor of the present application has previously invented a method for refining vegetable oil (virgin oil) or vegetable waste oil into fuel for diesel engines in order to improve the above-mentioned drawbacks of the methyl esterification technique. Open 2000-21988
No. 6).

In this method, water and ozone are allowed to act on a heated vegetable oil (virgin oil) or a vegetable waste oil to thereby remove impurities such as glycerin and animal fats and oils in the vegetable oil (virgin oil) or the vegetable waste oil. Is separated and removed. This method regenerates vegetable waste oil into diesel engine fuel, and does not mention fish waste oil. However, for fish and animal waste oils, some university laboratories have just started research on diesel engine fuels, and it will take a considerable amount of time to obtain results.

[0016]

SUMMARY OF THE INVENTION The present invention solves all of these problems, prevents environmental pollution, and contributes to global environmental improvement. That is, the present invention is for refining a fuel for a diesel engine from fish waste oil or the like, which prevents environmental pollution by the fish waste oil, cleans the exhaust gas of the diesel engine, and helps extend the life of mineral oil. .

Further, a new method is proposed for regenerating vegetable waste oil which has not become widespread due to the drawbacks of the methyl esterification technology, and it can be purified without using any chemicals. It can be purified by mixing. Furthermore, purification can be performed by mixing during purification. This is a refining technology that does not cause any problem even if the products purified independently of both fish waste oil and vegetable waste oil are mixed.

The plant construction is inexpensive, the production cost is low, and the market is competitive. A further object of the present invention is to provide a "method and apparatus for refining animal and vegetable oils (virgin oil) and animal and vegetable waste oils into fuel for diesel engines", which is regenerated into fuel of higher quality than light oil.

[0019]

For this reason, the present invention provides a stirring process while injecting ozone into fish oil (virgin oil or waste vegetable oil) or a mixture of the fish oil and vegetable oil (virgin oil or vegetable waste oil). An object of the present invention is to provide a method for producing a diesel engine fuel from waste oil containing animal waste oil (fish waste oil), which comprises adding an oxidation-reduction agent and a polymerization inhibitor during treatment.

Further, the present invention relates to a method for stirring a mixture of fish oil (virgin oil or waste fish oil) or a mixture of the above-mentioned fish oil and vegetable oil (virgin oil or vegetable waste oil) while injecting ozone. After the primary treatment of adding the polymerization inhibitor, the ozone treatment is performed again through the filtration step, and the secondary treatment is performed. This is a method for producing a diesel engine fuel.

In the present invention, fish oil (virgin oil or fish waste oil) or vegetable oil (virgin oil or vegetable waste oil) as a raw material is a raw material having various origins. Removal is preferred. These fish oils (virgin oil or fish waste oil)
Is obtained by mechanically squeezing from fish waste and filtering it.

The filtering material used in the filtration step to remove impurities in the raw material is activated clay, diatomaceous earth, zeolite, activated carbon, and bone ash, and is used in an amount of 20 to 25 kg per 1 liter of the raw material.

The concentration of ozone used in the injection of ozone is 500 to 30,000 ppm, and the desirable concentration is 2,000 to 10,000 ppm.

In the primary treatment, stirring is performed for 2 minutes per minute.
The stirring is performed at a speed of 50 to 1,000 rotations for 60 minutes, and the stirring in the secondary treatment is performed at a speed of 100 to 300 rotations per minute for 30 to 120 minutes.

The redox material is an iron compound such as a ferric oxide compound or a copper compound, and is added in an amount of 0.15 g per liter of the raw material.

The polymerization inhibitor is a phosphorus compound and is added in an amount of 0.2 g to 0.25 g per kiloliter of the raw material.

In order to prevent crystallization in winter, which is a drawback of the raw material, a crystallization inhibitor made of castor oil or the like is added during the secondary treatment. To 0.1% by weight.

Further, the plant additive for homogenizing the product is added in an amount of 2 to 5% by weight based on the raw material,
The product is stirred.

FIG. 6 shows an overall process flow of the method for producing a diesel engine fuel according to the present invention.

[0030]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for producing a diesel engine fuel according to the present invention will be described in detail.

The raw material of the present invention is fish oil (virgin oil or fish waste oil) or the above-mentioned fish oil and vegetable oil (virgin oil or vegetable waste oil).
, Which is used to produce diesel engine fuel oil. The entire steps of this production method will be described in more detail.

Pretreatment filtration step Primary treatment step Primary filtration step Secondary treatment step Secondary filtration step Product preconditioning step The above six steps will be described in detail with reference to the drawings.

[Pretreatment Filtration Step] There are various kinds of raw materials such as fish waste oil, vegetable oil, and vegetable waste oil. That is, since various impurities are mixed in according to the type of company, business establishment, and business contents which discharge raw materials (eg, ash, fish chips, meat chips, etc.), it is preferable to remove the mixed impurities. As the method, a pressure-type filter press or a suction-type filter is used. Activated clay, diatomaceous earth, zeolite, activated carbon, bone ash, etc. may be used as the type of filter medium used for filtration. It is also possible to use a mixture of different types of filter media. The amount of filter media used is raw material 1
20 kg to 25 kg per kiloliter.

FIG. 1 shows a pressurized filter press, and FIG. 2 shows a suction filter device.

The raw material that has passed through the pretreatment filtration step is removed from impurities and becomes a clean raw material, and is transferred to the primary processing apparatus.

[Primary treatment step] The raw material after the pretreatment filtration step is transferred to the primary treatment device.

FIG. 3 shows the primary processing apparatus. In the upper part of the primary treatment device, a raw material introduction port and a redox agent / polymerization inhibitor introduction port from the pretreatment filtration device are provided, and an ozone injection port is provided at the bottom of the inside of the device, and in the center of the device. A stir bar is provided. A propeller is attached to the stirring rod at a position slightly above the ozone inlet. The propeller is specially processed and has a saw-toothed eye around the tip of the propeller. Alternatively, a wire brush may be provided on the horizontal axis slightly above the ozone inlet. The purpose of this is to make the raw material the finest particles when stirring.
This is also for the purpose of making the ozone gas the finest particles. Further, in order to improve the stirring efficiency when stirring, ordinary stirring blades are mounted immediately above the special propeller or the horizontal wire brush. Further, it is preferable to provide an iron plate (also called a jammer plate) having a width of 10 cm to 15 cm and having a band-shaped saw-toothed shape from the top to the lowest part at four places on the outer wall inside the primary processing apparatus.

In such a primary processing apparatus, the raw material passed through the pretreatment filtration device is introduced from the upper raw material introduction port,
Ozone is taken in from the lower ozone inlet. The ozone concentration used is 500 to 30,000 ppm. The desirable ozone concentration in these ozone injection concentration ranges is 2,000 ppm to 10,000 ppm.

These materials are well stirred. Originally, the stirring speed is desirably 10,000 to 30,000 revolutions per minute. However, from the viewpoint of work safety, there is a high danger.
Here, a desirable rotation speed in the stirring is 250 to 350 rotations per minute. Solving the problem of ultra-high-speed rotation by using a saw blade-shaped eye on the propeller or performing special processing or using countless needle-shaped wire brushes to achieve the same performance as 10,000 to 30,000 rotations It was done. In addition, natural electromagnetic waves are generated in the raw material as an effect of the super high-speed rotation ability. As a result, the ozonolysis reaction is quickly and reliably performed.

By the agitation, the raw material and ozone which have been made into the finest particles are mixed with each other to promote oxidation of the raw material, and glycerin and fatty acid in the raw material are separated from the raw material, decomposed and suspended. This is called destruction or cracking of the raw material.
However, the oxidation is suppressed by adding 0.15 g of a redox agent per liter of the raw material so that the raw material does not become excessively oxidized, and the saturated fatty acid is converted into an unsaturated fatty acid by ozonolysis, that is, an olefin effect is produced and converted into ozonide. Go. Ozonide is formed into aldehydes and ketones by the reducing agent and becomes a state that easily becomes fuel. In case of excessive oxidation, the raw material may cause a polymerization reaction. Therefore, 0.2 to 0.25 g of a polymerization inhibitor is added per 1 kL of the raw material. This processing step is performed for 60 minutes.

[Primary filtration step] In this step, a pressure filter press or suction filtration is performed. The apparatus used in this step is exactly the same as that in FIGS. 1 and 2 shown as the pretreatment filtration apparatus. The purpose of the filtration is to remove glycerin, fatty acids, etc., which are the purified substances extracted from the raw materials by the primary treatment, and the redox agent and the polymerization inhibitor used in the reaction. The filter medium used in this step may be any of activated clay, diatomaceous earth, zeolite, activated carbon, bone ash and the like. Alternatively, various types of filtering materials may be used in combination. The amount of the filter agent used is from 20 kg to 25 kg per 1 kL of the raw material. The raw material that has passed through the primary filtration step becomes a highly accurate raw material, and the flammability is as high as that of mineral oil, and the ignitability comes out after this filtration step.

[Secondary Treatment Step] The raw material after the primary filtration step is transferred. The secondary treatment device is the same as the primary treatment device, and has an ozone inlet at the bottom of the device. Then, a stirrer and a jammer plate having the same shape as that of the primary treatment device are provided at the same position (see FIGS. 3 and 4). The raw material that has passed through the primary filtration device is introduced into this secondary treatment device, and ozone is taken in from the ozone inlet at the lowest part of the secondary treatment device and stirred. Ozone concentration is 500 to 30,000 pp
m, and a desirable concentration is 2,000 to 10,000.
It is 0 ppm. The stirring speed is 100 to 300 rotations per minute, but may be 200 to 300 rotations per minute. Preferably, only the bubbling of the ozone flow rate may be performed.
The purpose of the secondary treatment is to use a primary treatment device in which the particles of the raw material are converted to the finest particles to further reduce the particles to ultrafine particles, whereby complete combustion occurs when used in an internal combustion engine.

A crystallization inhibitor is added in an amount of 0.05 to 0.1% by weight of the raw material for preventing crystallization in winter, which is a disadvantage of the raw material. Castor oil or the like is used as a crystallization inhibitor.
In addition, the decolorizing and deodorizing effects, which are the features of ozone, appear. The processing time of the secondary processing device is 60 to 90 minutes,
Alternatively, it may be for 30 to 120 minutes.

[Secondary Filtration Step] The raw material after the secondary treatment step is passed through the secondary filtration step.

For the purpose of the present invention, in the case of a suspended matter remaining in the stage of the primary treatment step, and the suspended matter is newly extracted by the secondary treatment apparatus, the suspended matter is removed in the secondary filtration step.
And improve the accuracy of the product.

The filter medium used is activated clay, diatomaceous earth,
Any of zeolite, activated carbon and bone ash may be used. Alternatively, various types of filtering materials may be used in combination.

[Pre-Product Adjustment Step] The raw material before the product that has passed through the secondary filtration device is transferred to the product pre-conditioning device. As shown in FIG. 5, the product preconditioning device is a tank having a stirrer at the center of the device, and has a material and additive introduction port at an upper portion and a product takeout port at a lower portion. In this step, the raw material passed through the secondary filtration device is finally adjusted as fuel for a diesel engine.

Although the raw material that has passed through the secondary filtration device is almost in a state close to a product, the raw material has a wide variety of oils.
Add additive extracted from plant raw material to homogenize product.
Then, the mixture is stirred for 30 minutes. The stirring may be carried out using ordinary blades, and the stirring speed may be 150 to 200 revolutions per minute.

At the end of this step, the fuel is complete for a diesel engine.

Table 1 shows the analysis results of one example of the analysis of the fuel purified from the present invention after the completion of this step.

[0051]

[Table 1]

As can be clearly seen from the above table, it is clear that the fuel purified by the technique of the present invention (revived fuel in the table) has higher accuracy than the methyl esterification method EU standard in Japan. In particular, when compared with a certain company that is actually refining in Japan, the difference in accuracy is apparent. In the analysis as a fuel, the numerical value of the distillation test result is important. As shown in the table, in the distillation test, the value of the revive fuel is superior to that of Idemitsu light oil. This may indicate how liquid particles are minimized as fuel. Minimizing fuel particles means that when used in an internal combustion engine, incomplete combustion can be prevented and complete combustion can be achieved. Complete combustion eliminates harmful substances in exhaust gas and no generation of graphite. Therefore, he is convinced that improvement of environmental pollution due to exhaust gas discharged from diesel engines, which has become a social problem, can be expected. Next, the present invention will be described more specifically with reference to examples.

Fish waste liquid and fish oil (virgin oil) mechanically squeezed out of fish waste and used are used as raw materials.
Using 1 kl of this raw material, impurities such as fish dust and impurities are removed using a pressure filter press. At that time, activated clay was used as a filter medium. The raw material (fish oil, fish waste oil) from which impurities have been removed is transferred to the primary treatment device. In the primary treatment apparatus, as shown in FIG. 3, raw materials are charged from the upper part of the treatment tank, and the ozone concentration of 2,000 is supplied from the lower ozone inlet.
0 to 10,000 ppm is supplied with stirring. During the stirring, a ferric oxide compound is added as a redox agent, and a phosphorus compound is added as a polymerization inhibitor, and the mixture is treated for about 60 minutes. The rotation speed of the stirrer was 500 to 1,000 rotations per minute. After the primary treatment, the raw material is transferred to a primary filtration device to remove impurities such as glycerin and fatty acids generated by the reaction.

The raw material that has passed through the primary filtration device is transferred to a secondary treatment device, and ozone is injected from an ozone injection port at the bottom of the device. Ozone concentration is 2,000 to 10,000pp
m, the stirring speed is 200 to 400 revolutions / min.
Castor oil is added as a crystallization inhibitor of 0.05 to 0.1% by weight of the raw material. Processing time was 60 to 90 minutes. The raw material after the secondary treatment is passed through a secondary filtration device to improve the commercialization. The filter medium was activated clay. After passing through the secondary filtration device, it is transferred to a product pre-conditioning device, and 2 to 5% by weight of a plant additive is added to the raw material to add about 3%.
Stir for 0 minutes. As a result, a final product aimed at by the present invention was obtained.

[0055]

As described in detail above, the present invention provides:
Using diesel waste oil or a mixture of vegetable waste oil and fish waste oil, which has been conventionally discarded, as a raw material, a diesel engine fuel of the same quality as or better than that of a diesel engine manufactured from conventional mineral resources can be produced at a lower cost. It was realized to be manufactured.

[Brief description of the drawings]

FIG. 1 shows an example of a pretreatment filtration device using a pressure type filter press used in a method for producing a diesel engine fuel according to the present invention.

FIG. 2 shows an example of a pretreatment filtration device of a suction type filtration device used in the method for producing a diesel engine fuel according to the present invention.

FIG. 3 shows an example of a propeller type primary treatment apparatus used in the method for producing a diesel engine fuel according to the present invention.

FIG. 4 shows an example of a brush type primary treatment apparatus used in the method for producing a diesel engine fuel according to the present invention.

FIG. 5 shows an example of a product preconditioning device used in the method for producing fuel for a diesel engine according to the present invention.

FIG. 6 shows an overall process flow of a method for producing a diesel engine fuel according to the present invention.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 4, 2002 (2002.4.4)

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction contents]

[Document Name] Statement

Patent application title: Method for producing fuel for diesel engine

[Claims]

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a diesel engine fuel from a substance other than mineral oil such as petroleum, coal or natural gas, and more particularly to a fish oil (virgin oil or fish waste oil) or a mixture of said fish oil and vegetable oil. (Virgin oil or vegetable waste oil).

[0002]

2. Description of the Related Art Naturally, the reserves of fossil fuels or mineral oils, such as oil, coal, or natural gas, which are buried on the earth are limited. It is feared that it will be depleted in decades.

On the other hand, it is said that the amount of fish and the like discarded after being harvested and used for food, feed, fertilizer, etc., ranges from 10 million to 15 million tons in one year in Japan alone. It is estimated that at least ten times more than this is discarded in the world. A part of such fish waste is further mechanically squeezed into solid or powder, and is used as feed for livestock and fertilizers for growing agricultural crops.

[0004] Until a few years ago, most of the effluents generated when squeezing fish wastes were dumped in the ocean. However, this has been a factor in marine pollution, and there has been a growing awareness of the need to protect the global environment. Marine dumping of fish waste is being banned in various countries, and related companies and organizations are currently struggling to dispose of such fish waste.

[0005] After banning the dumping of fish waste into the ocean, there is an example in which the waste liquid squeezed out of fish waste is mixed with heavy oil A and burned for boilers for incineration. It is one of the causes of environmental pollution. In addition, there are many difficult problems that have led to the failure of the boiler kettle.

[0006] The amount of fish waste emissions in Japan is 100
Of the 10,000 to 15 million tons, it is said that 4 to 4.5 million tons of mechanically pressed fish waste oil is discharged annually. When considering environmental pollution on a global level, it is urgent to consider this solution.

[0007] Furthermore, in Japan, the emission amount of vegetable waste oil (waste cooking oil) is publicly announced, about 200,000 tons per year from companies such as the catering industry and food processing factories, and about 200,000 tons from ordinary households, for a total of 400,000 tons. It is said that.

[0008] Vegetable oil manufacturers ship 1 edible oil.
It is estimated that the amount of vegetable oil is in the range of 100,000 to 1.5 million tons, which indicates that the amount of vegetable oil actually emitted is much higher. Environmental pollution caused by this vegetable waste oil (waste cooking oil) has been highlighted as a social problem, and solutions are urgently needed.

[0009] The types of vegetable waste oil (waste cooking oil) are roughly classified into four types.
There are types. Upper waste oil, middle waste oil, lower waste oil, and sludge. At present, the treatment and disposal methods of vegetable waste oil (waste cooking oil) are as follows. Some of the upper waste oil is reused as feed, soap and food for livestock (it was banned from exporting overseas). A portion of the upper waste oil was used as fuel for diesel engines using methyl esterification technology. Have been. The intermediate waste oil, lower waste oil, and sludge are incinerated by industrial waste intermediate treatment companies using auxiliary fuel. Waste oil from homes is solidified using a solidifying temple agent and is disposed of at municipal incineration plants. In addition, it has been reported as an environmental pollution issue in newspapers etc. by illegal dumping by other vicious companies. In some cases, household waste oil is being flushed from the kitchen sink.

Although there is no real solution to this problem as environmental improvement is called out on a global level, each company, each government, and each local government are currently struggling, but environmental problems that need to be resolved immediately It is.

In recent years, part of vegetable waste oil has been recycled as a fuel for diesel engines by the so-called “methyl esterification technology”. In this technology, first, methanol or ethanol is added to vegetable waste oil (upper waste oil) in an amount of about 30% by weight of the raw material, and subsequently, sodium hydroxide is used as a catalyst in an amount of 1% to 1. Mix 5% and stir. After standing for a while, it is separated into impurities (impurities, water, free fatty acids) with a specific gravity difference, and the upper oil portion is taken out.

[0012] By adding sodium hydroxide to the portion of the oil taken out, transesterification is carried out to form an ester layer and waste glycerin. The portion of the ester layer is refined to be a methyl esterified fuel, while the portion of waste glycerin is neutralized and decomposed by-products and disposed of by an industrial waste trader for a fee.

However, this methyl esterified fuel technology has the following problems. 1. Production cost is high because 30% to 50% of alcohol (methanol or ethanol) is added to the raw material (vegetable waste oil). 2. Plant construction costs are high due to disaster prevention because a large amount of alcohol is used. 3. There is a problem with work safety. 4. Poor yield after purification. Also, only the upper waste oil can be refined among the waste oils. 5. When alcohol and sodium hydroxide are used, if used as fuel, formaldehyde,
Acrolein, benzene, etc. are not clean fuels because they emit more than when diesel is used. 6. Since alcohol is used, trouble easily occurs inside the piston, piston ring, and head inside the diesel engine. 7. Medium waste oil, lower waste oil and sludge cannot be refined, so they are not useful for environmental improvement.

Therefore, the inventor of the present application has previously invented a method for refining vegetable oil (virgin oil) or vegetable waste oil into fuel for diesel engines in order to improve the above-mentioned drawbacks of the methyl esterification technique. Open 2000-21988
No. 6).

In this method, water and ozone are allowed to act on a heated vegetable oil (virgin oil) or a vegetable waste oil to thereby remove impurities such as glycerin and animal fats and oils in the vegetable oil (virgin oil) or the vegetable waste oil. Is separated and removed. This method regenerates vegetable waste oil into diesel engine fuel, and does not mention fish waste oil. However, for fish and animal waste oils, some university laboratories have just started research on diesel engine fuels, and it will take a considerable amount of time to obtain results.

[0016]

SUMMARY OF THE INVENTION The present invention solves all of these problems, prevents environmental pollution, and contributes to global environmental improvement. That is, the present invention is for refining a fuel for a diesel engine from fish waste oil or the like, which prevents environmental pollution by the fish waste oil, cleans the exhaust gas of the diesel engine, and helps extend the life of mineral oil. .

Further, a new method is proposed for regenerating vegetable waste oil which has not become widespread due to the drawbacks of the methyl esterification technology, and it can be purified without using any chemicals. It can be purified by mixing. Furthermore, purification can be performed by mixing during purification. This is a refining technology that does not cause any problem even if the products purified independently of both fish waste oil and vegetable waste oil are mixed.

The plant construction is inexpensive, the production cost is low, and the market is competitive. A further object of the present invention is to provide a "method and apparatus for refining animal and vegetable oils (virgin oil) and animal and vegetable waste oils into fuel for diesel engines", which is regenerated into fuel of higher quality than light oil.

[0019]

For this reason, the present application relates to a method for producing a fish oil (virgin oil or fish waste oil) or a filtered mixture of the fish oil and vegetable oil (virgin oil or vegetable waste oil) (hereinafter referred to as "raw material"). The raw material is finely divided by stirring at a rotation speed necessary to destroy the composition of the raw material and cause a cracking phenomenon while introducing ozone, so that the raw material does not become excessively oxidized during the stirring processing. An object of the present invention is to provide a method for producing a diesel engine fuel, which comprises adding an oxidation-reduction agent and a polymerization inhibitor.

[0020] The present invention also provides a method for converting the raw material into fine particles by subjecting the raw material to fine particles by subjecting the raw material to a stirring treatment at a rotation speed necessary to destroy the composition of the raw material and cause a cracking phenomenon. Primary processing steps;
Filtering the product obtained by the primary treatment,
Each step of a secondary processing step of stirring while injecting ozone to further re-micronize the filtered one, and a step of adding a crystal inhibitor to the one obtained by the secondary processing step, Having, in the primary processing step,
An object of the present invention is to provide a method for producing a diesel engine fuel, which comprises adding an oxidation-reduction agent and a polymerization inhibitor so that the raw material does not become excessively oxidized.

Here, the rotation speed required for destroying the composition of the raw material in the stirring process to cause a cracking phenomenon is substantially at least 10,000 rotations per minute.

The fish oil is obtained by squeezing fish or fish waste and filtering it. The filtering material used in the filtering step is activated clay, diatomaceous earth, zeolite, activated carbon, and bone ash, and is characterized in that 20 to 25 kg is used for 1 kiloliter of the raw material.

[0023] The concentration of ozone used in the stirring process is 2,000 to 10,000 ppm.

The redox agent is an iron compound such as a ferric oxide compound or a copper compound, and is added in an amount of 0.15 g per kiloliter of the raw material. The compound is characterized in that 0.2 g to 0.25 g is added per kiloliter of the raw material.

Further, the crystallization inhibitor is characterized in that it is 0.05 to 0.1% by weight based on the raw material.

The present invention further relates to a processing apparatus for producing a fuel for a diesel engine from fish oil (virgin oil or fish waste oil) or a filtered mixture of said fish oil and vegetable oil (virgin oil or vegetable waste oil). A processing apparatus body, a raw material input port for charging the raw material into the processing apparatus main body, an ozone input port for charging ozone into the processing apparatus main body, an oxidation-reduction agent and a polymerization inhibitor. A chemical inlet for charging into the processing apparatus main body, and the raw material, the ozone, the redox agent, and the polymerization inhibitor are stirred in the processing apparatus main body to destroy the composition of the raw material and crack. Stirring means for causing a phenomenon, wherein the stirring means is a propeller means for rotating and stirring the raw material and the like in the processing apparatus body. There is provided a processing apparatus for producing a fuel for diesel engines, characterized in that it is composed of a saw-th cored stirred auxiliary means provided on the inside of the processing apparatus main body.

Here, the propeller means is a saw bladed propeller or an infinite number of needle-shaped wire brushes, and the rotation speed of the propeller means is 250 to 350 rotations per minute. It has a stirring ability substantially equivalent to stirring at least 10,000 revolutions per minute.

[0028]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for producing a diesel engine fuel according to the present invention will be described in detail. FIG. 6 shows the overall process flow of the method for producing a diesel engine fuel according to the present invention.

The raw material of the present invention is fish oil (virgin oil or fish waste oil) or the above-mentioned fish oil and vegetable oil (virgin oil or vegetable waste oil).
, Which is used to produce diesel engine fuel oil. The entire steps of this production method will be described in more detail.

Pretreatment filtration step Primary treatment step Primary filtration step Secondary treatment step Secondary filtration step Product preconditioning step The above six steps will be described in detail with reference to the drawings.

[Pretreatment Filtration Step] There are various kinds of raw fish waste oil, vegetable oil, and vegetable waste oil. That is, since various impurities are mixed in according to the type of company, business establishment, and business contents which discharge raw materials (eg, ash, fish chips, meat chips, etc.), it is preferable to remove the mixed impurities. As the method, a pressure-type filter press or a suction-type filter is used. Activated clay, diatomaceous earth, zeolite, activated carbon, bone ash, etc. may be used as the type of filter medium used for filtration. It is also possible to use a mixture of different types of filter media. The amount of filter media used is raw material 1
20 kg to 25 kg per kiloliter.

FIG. 1 shows a pressurized filter press, and FIG. 2 shows a suction filter device.

The raw material that has passed through the pretreatment filtration step is removed from impurities and becomes a clean raw material, and is transferred to the primary processing apparatus.

[Primary treatment step] The raw material after the pretreatment filtration step is transferred to the primary treatment device.

FIG. 3 shows the primary processing apparatus. In the upper part of the primary treatment device, a raw material introduction port and a redox agent / polymerization inhibitor introduction port from the pretreatment filtration device are provided, and an ozone injection port is provided at the bottom of the inside of the device, and in the center of the device. A stir bar is provided. A propeller is attached to the stirring rod at a position slightly above the ozone inlet. The propeller is specially processed and has a saw-toothed eye around the tip of the propeller. Alternatively, a wire brush may be provided on the horizontal axis slightly above the ozone inlet. The purpose of this is to make the raw material the finest particles when stirring.
Also, this is because the ozone gas is also converted to the finest particles. Further, in order to improve the stirring efficiency when stirring, ordinary stirring blades are mounted immediately above the special propeller or the horizontal shaft wire brush. Further, it is preferable to provide an iron plate (also referred to as a jammer plate) having a width of 10 cm to 15 cm and having a band-shaped sawtooth-shaped eye from the upper portion to the lowermost portion at four locations on the outer wall inside the primary processing apparatus.

In such a primary treatment apparatus, the raw material that has passed through the pretreatment filtration device is introduced from the upper raw material introduction port,
Ozone is taken in from the lower ozone inlet. The ozone concentration used is 500 to 30,000 ppm. The desirable ozone concentration in these ozone injection concentration ranges is 2,000 ppm to 10,000 ppm.

These materials are stirred well. Originally, the stirring speed is desirably 10,000 to 30,000 revolutions per minute. However, from the viewpoint of work safety, there is a high danger. Therefore, the stirring speed is set to 250 to 350 revolutions per minute or 500 to 1,000 revolutions per minute.
Here, a desirable rotation speed in the stirring is 250 to 350 rotations per minute. Solving the problem of ultra-high-speed rotation by using a saw blade-shaped eye on the propeller or performing special processing or using countless needle-shaped wire brushes to achieve the same performance as 10,000 to 30,000 rotations It was done. In addition, natural electromagnetic waves are generated in the raw material as an effect of the super high-speed rotation ability. As a result, the ozonolysis reaction is quickly and reliably performed.

By stirring, the raw material and ozone which have been made into the finest particles are mixed with each other to promote oxidation of the raw material, and glycerin and fatty acid in the raw material are separated, decomposed and suspended from the raw material. This is called destruction or cracking of the raw material.
However, oxidation suppression is performed by adding 0.15 g of a redox agent per liter of raw material so that the raw material does not become excessively oxidized, and ozonolysis converts saturated fatty acids into unsaturated fatty acids, that is, produces an olefin effect and changes into ozonide. Go. Ozonide is formed into aldehydes and ketones by the reducing agent and becomes a state that easily becomes fuel. In case of excessive oxidation, the raw material may cause a polymerization reaction. Therefore, 0.2 to 0.25 g of a polymerization inhibitor is added per 1 kL of the raw material. This processing step is performed for 60 minutes.

[Primary filtration step] In this step, a pressure filter press or suction filtration is performed. The apparatus used in this step is exactly the same as that in FIGS. 1 and 2 shown as the pretreatment filtration apparatus. The purpose of the filtration is to remove glycerin, fatty acids, etc., which are purified substances extracted from the raw materials by the primary treatment, and the redox agent and the polymerization inhibitor used in the reaction. The filter medium used in this step may be any of activated clay, diatomaceous earth, zeolite, activated carbon, bone ash and the like. Alternatively, various types of filtering materials may be used in combination. The amount of the filter agent used is from 20 kg to 25 kg per 1 kL of the raw material. The raw material that has passed through the primary filtration step becomes a highly accurate raw material, and the flammability is as high as that of mineral oil, and the ignitability comes out after this filtration step.

[Secondary treatment step] The raw material after the primary filtration step is transferred. The secondary treatment device is the same as the primary treatment device, and has an ozone inlet at the bottom of the device. Then, a stirrer and a jammer plate having the same shape as that of the primary treatment device are provided at the same position (see FIGS. 3 and 4). The raw material that has passed through the primary filtration device is introduced into this secondary treatment device, and ozone is taken in from the ozone inlet at the lowest part of the secondary treatment device and stirred. Ozone concentration is 500 to 30,000 pp
m, and a desirable concentration is 2,000 to 10,000.
It is 0 ppm. The stirring speed is 100 to 300 rotations per minute, but may be 200 to 300 rotations per minute. Preferably, only the bubbling of the ozone flow rate may be performed.
The purpose of the secondary treatment is to treat the raw material particles in the primary treatment device, which has been converted to the finest particles, further into ultrafine particles, whereby complete combustion occurs when used in an internal combustion engine.

A crystallization inhibitor of 0.05 to 0.1% by weight of the raw material is added to prevent crystallization in winter, which is a disadvantage of the raw material. Castor oil or the like is used as a crystallization inhibitor.
In addition, the decolorizing and deodorizing effects, which are the features of ozone, appear. The processing time of the secondary processing device is 60 to 90 minutes,
Alternatively, it may be for 30 to 120 minutes.

[Secondary Filtration Step] The raw material after the secondary treatment step is passed through the secondary filtration step.

For the purpose, in the case of a suspended matter remaining in the stage of the primary treatment step, and a suspended matter is newly extracted by the secondary treatment device, the suspended matter is removed in the secondary filtration step.
And improve the accuracy of the product.

The filter medium used is activated clay, diatomaceous earth,
Any of zeolite, activated carbon and bone ash may be used. Alternatively, various types of filtering materials may be used in combination.

[Pre-Product Adjustment Step] The raw material before the product that has passed through the secondary filtration device is transferred to the product pre-conditioning device. As shown in FIG. 5, the product preconditioning device is a tank having a stirrer at the center of the device, and has a material and additive introduction port at an upper portion and a product takeout port at a lower portion. In this step, the raw material passed through the secondary filtration device is finally adjusted as fuel for a diesel engine.

Although the raw material that has passed through the secondary filtration device is almost in a state close to a product, the raw material has a wide variety of oils.
Add additive extracted from plant raw material to homogenize product.
Then, the mixture is stirred for 30 minutes. The stirring may be carried out using ordinary blades, and the stirring speed may be 150 to 200 revolutions per minute.

At the end of this step, the fuel is complete for a diesel engine.

Table 1 shows the analysis results of one example of the analysis of the fuel purified from the present invention after the completion of this step.

[0049]

[Table 1]

As can be clearly seen from the above table, it is clear that the fuel refined by the technique of the present invention (revived fuel in the table) has higher accuracy than the methyl esterification method EU standard in Japan. In particular, when compared with a certain company that is actually refining in Japan, the difference in accuracy is apparent. In the analysis as a fuel, the numerical value of the distillation test result is important. As shown in the table, in the distillation test, the value of the revive fuel is superior to that of Idemitsu light oil. This may indicate how liquid particles are minimized as fuel. Minimizing fuel particles means that when used in an internal combustion engine, incomplete combustion can be prevented and complete combustion can be achieved. Complete combustion eliminates harmful substances in exhaust gas and no generation of graphite. Therefore, he is convinced that improvement of environmental pollution due to exhaust gas discharged from diesel engines, which has become a social problem, can be expected. Next, the present invention will be described more specifically with reference to examples.

A fish waste liquid and fish oil (virgin oil) mechanically squeezed out of fish waste and used are used as raw materials.
Using 1 kl of this raw material, impurities such as fish debris and impurities are removed using a pressure filter press. At that time, activated clay was used as a filter medium. The raw material (fish oil, fish waste oil) from which impurities have been removed is transferred to the primary treatment device. In the primary treatment apparatus, as shown in FIG. 3, raw materials are charged from the upper part of the treatment tank, and the ozone concentration of 2,000 is supplied from the lower ozone inlet.
To 10,000 ppm with stirring. During the stirring, a ferric oxide compound is added as a redox agent, and a phosphorus compound is added as a polymerization inhibitor, and the mixture is treated for about 60 minutes.
In addition, the rotation speed of the stirrer is 500 to 1,000 rotations /
One minute. After the primary treatment, the raw material is transferred to a primary filtration device to remove impurities such as glycerin and fatty acids generated by the reaction.

The raw material that has passed through the primary filtration device is transferred to a secondary treatment device, and ozone is injected from an ozone injection port at the bottom of the device. Ozone concentration is 2,000 to 10,000pp
m, the stirring speed is 200 to 400 revolutions / min.
Castor oil is added as a crystallization inhibitor of 0.05 to 0.1% by weight of the raw material. Processing time was 60 to 90 minutes. The raw material after the secondary treatment is passed through a secondary filtration device to improve the commercialization. The filter medium was activated clay. After passing through the secondary filtration device, it is transferred to a product pre-conditioning device, and 2 to 5% by weight of a plant additive is added to the raw material to add about 3%.
Stir for 0 minutes. As a result, a final product aimed at by the present invention was obtained.

[0053]

As described in detail above, the present invention provides:
Using diesel waste oil or a mixture of vegetable waste oil and fish waste oil, which has been conventionally discarded, as a raw material, a diesel engine fuel of the same quality as or better than that of a diesel engine manufactured from conventional mineral resources can be produced at a lower cost. It was realized to be manufactured.

[Brief description of the drawings]

FIG. 1 shows an example of a pretreatment filtration device using a pressure type filter press used in a method for producing a diesel engine fuel according to the present invention.

FIG. 2 shows an example of a pretreatment filtration device of a suction type filtration device used in the method for producing a diesel engine fuel according to the present invention.

FIG. 3 shows an example of a propeller type primary treatment apparatus used in the method for producing a diesel engine fuel according to the present invention.

FIG. 4 shows an example of a brush type primary treatment apparatus used in the method for producing a diesel engine fuel according to the present invention.

FIG. 5 shows an example of a product preconditioning device used in the method for producing fuel for a diesel engine according to the present invention.

FIG. 6 shows an overall process flow of a method for producing a diesel engine fuel according to the present invention.

Claims (11)

[Claims] 1. A stirring treatment is carried out while injecting ozone into fish oil (virgin oil or fish waste oil) or a mixture of said fish oil and vegetable oil (virgin oil or vegetable waste oil) (hereinafter referred to as “raw material”). A method for producing a fuel for a diesel engine, comprising adding an oxidation-reduction agent and a polymerization inhibitor into the fuel. 2. A stirring treatment is carried out while injecting ozone into fish oil (virgin oil or fish waste oil) or a mixture of said fish oil and vegetable oil (virgin oil or vegetable waste oil) (hereinafter referred to as “raw material”). A primary treatment step of introducing an oxidation-reduction agent and a polymerization inhibitor therein; a secondary treatment step of filtering a substance obtained by the primary treatment and performing a stirring treatment while injecting ozone again; A method for producing a fuel for a diesel engine, comprising the steps of: adding a plant additive to the product obtained by the treatment step; 3. The method for producing a diesel engine fuel according to claim 1, wherein the fish oil is obtained by squeezing fish or fish waste and filtering the same. 4. The filter medium includes activated clay, diatomaceous earth,
3. The method for producing a diesel engine fuel according to claim 1, wherein zeolite, activated carbon, and bone ash are used in an amount of 20 to 25 kg per 1 liter of the raw material. 5. The method for producing fuel for a diesel engine according to claim 1, wherein the concentration of ozone used in the ozone injection treatment is 2,000 to 10,000 ppm. 6. The stirring in the primary treatment step,
The stirring is performed at a speed of 250 to 1,000 rotations per minute for 60 minutes, and the stirring in the secondary treatment step is performed at a speed of 100 to 300 rotations per minute for 30 minutes to 12 minutes.
3. The method for producing fuel for a diesel engine according to claim 2, which is performed for 0 minutes. 7. The method according to claim 1, wherein the redox material is an iron compound such as a ferric oxide compound or a copper compound, and is added in an amount of 0.15 g per kiloliter of the raw material. 3. The method for producing a diesel engine fuel according to item 2. 8. The diesel engine fuel according to claim 1, wherein the polymerization inhibitor is a phosphorus compound and is added in an amount of 0.2 g to 0.25 g per kiloliter of the raw material. Production method. 9. The method for producing a diesel engine fuel according to claim 2, wherein a crystallization inhibitor is further added during the secondary treatment step. 10. The method according to claim 9, wherein the amount of the crystallization inhibitor is 0.05 to 0.1% by weight based on the raw material. 11. The method according to claim 2, wherein 2 to 5% by weight of the plant additive is added to the raw material and stirred.