JP2007211139A - Method and apparatus for producing fatty acid ester and glycerin, and fuel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a fatty acid ester and glycerin, which method effectively recovers and utilizes, by a simple and easy operation, an alcohol etc. used for reaction when a fatty acid ester usable as a diesel fuel etc. is produced from an edible oil and/or a waste edible oil. <P>SOLUTION: The method and apparatus for producing a fatty acid ester and glycerin comprises a pretreatment process for mixing an edible oil and/or a waste edible oil with an alkaline substance and glycerin containing an alcohol; a pretreated liquid separation process for separating a pretreated liquid obtained by the pretreatment process into the edible oil and/or the waste edible oil and glycerin; a transesterification process for forming a fatty acid ester and glycerin by performing transesterification by mixing the edible oil and/or the waste edible oil obtained by the pretreatment process with an alcohol in the presence of an alkali catalyst; and a reaction liquid separation process for separating the reaction liquid after the transesterification into a fatty acid ester and glycerin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention provides a method and apparatus for producing fatty acid ester and glycerin by reacting edible oil and / or waste edible oil with alcohol, which makes it possible to effectively utilize alcohol as a raw material for the reaction, and production thereof The present invention relates to a fuel containing a fatty acid ester produced by the method.

  Conventionally, petroleum-based fossil fuels such as gasoline, heavy oil, light oil and the like have been used in various fields. However, these petroleums simultaneously produce harmful sulfur oxides as exhaust gas during combustion, which causes air pollution. Therefore, development of energy sources with less pollution has been desired.

  Therefore, oils and fats such as rapeseed oil, fatty oil and glycerin ester, edible oil such as palm oil, soybean oil, sesame oil, corn oil, safflower oil do not contain sulfur, and are attracting attention as a new energy source with little air pollution. A method for obtaining a fatty acid ester useful as a fuel from these edible oils or waste edible oils after using them has been studied.

  Furthermore, in response to the recent trend of restricting the use of fossil fuels from the viewpoint of protecting the global environment and the growing demand for replacement of diesel fuel oil due to the protracted rise in crude oil prices, a method for producing fuel from edible oil or waste edible oil From the viewpoint of cost reduction and effective use of resources, many reports on fuel production are currently being made.

  For example, in order to continuously produce fatty acid esters, in order to continuously produce higher fatty acid methyl esters from waste cooking oil, specific gravity separation while slowing the flow of reaction products after reaction in a high temperature region A method and an apparatus (see Patent Document 1) that can continuously reduce glycerin and higher fatty acid methyl ester by a separator having a flow path to reduce production cost by automation, and non-fossil oil and fat. In the production of an alternative fuel containing glycerin by reacting an aromatic alcohol, a method and an apparatus having a glycerin separation tank for standing the reaction product and separating glycerin from the alternative fuel product (see Patent Document 2) )It has been known. Patent Document 2 further describes that mass production is possible by continuously supplying raw materials at a constant rate, and direct sales and supply to the market are possible by weighing.

In addition, as resources that effectively use resources, for example, after separating diesel fuel by transesterifying waste edible oil with methanol, from that by-product, separating and recovering and purifying glycerol, methanol is separated, The remaining fatty acid is subjected to esterification and neutralization reaction with higher fatty acid again with methanol to separate and purify by-products effective as heavy oil burner fuel (see Patent Document 3), and waste edible oil as a raw material After removing the solid substance from the solid substance by heating means and heating it, pre-treatment to evaporate and remove moisture and odorous substance by dehydration and deodorizing means, and solid adsorption from the light liquid containing the purified fatty acid alkyl ester A device for adsorbing and refining impurities with an agent (see Patent Document 4), and further, fatty acid from waste cooking oil and alcohol In preparing the ester, the method of manufacturing diesel fuel and that available as incinerator fuel (see Patent Document 5), and the like by reducing the glycerin alkali catalyst amount have been discarded hitherto.
Japanese Patent No. 3533061 JP 2001-98284 A Japanese Patent No. 3028282 Japanese Patent Laid-Open No. 10-231497 JP 2003-96473 A

  As described above, various techniques for promoting the effective use of resources have been studied in the method of producing fatty acid esters and glycerin by transesterifying edible oil or waste edible oil with alcohol. The use of glycerin as a by-product cannot be used, and a method for making more effective use of these resources has been demanded.

  Therefore, the present invention makes it possible to effectively use the excess alcohol contained in the glycerin separated after the transesterification reaction with a simple operation for the alcohol used in the reaction, and to effectively utilize the resources. An object of the present invention is to provide a method for producing a fatty acid ester.

  As a result of diligent research to solve the above problems, the present inventor has two stages of edible oil as a raw material when producing a useful fatty acid ester that can be used for diesel fuel or the like from edible oil and / or waste edible oil. It was found that the surplus alcohol previously added during the transesterification reaction can be used for a new reaction and resources can be effectively used by performing the treatment separately, and the present invention has been completed.

  That is, the method for producing a fatty acid ester and glycerin according to the present invention includes a edible oil and / or a waste edible oil mixed with glycerin containing alcohol and an alkaline substance, an edible oil obtained in the pretreatment step, and / Waste edible oil is mixed with alcohol in the presence of an alkali catalyst to undergo a transesterification reaction to produce a fatty acid ester and glycerin, and the reaction liquid after the transesterification reaction is a fatty acid ester layer and glycerin. And a reaction liquid separation step of separating into layers. At this time, a pretreatment liquid separation step of separating the pretreatment liquid obtained in the pretreatment step into an edible oil and / or a waste edible oil layer and a glycerin layer may be performed.

  The apparatus for producing fatty acid ester and glycerin according to the present invention includes a pretreatment means for mixing edible oil and / or waste edible oil with glycerin containing alcohol and an alkaline substance, and a pretreatment liquid obtained by the pretreatment means. Is separated into edible oil and / or waste edible oil and glycerin, and the edible oil and / or waste edible oil obtained by the pretreated liquid separation means are mixed with alcohol in the presence of an alkali catalyst. A transesterification reaction means for performing a transesterification reaction by mixing to produce a fatty acid ester and glycerin, and a reaction liquid separation means for separating the reaction liquid after the transesterification reaction into a fatty acid ester and glycerin. To do.

  The fuel of the present invention contains the fatty acid ester obtained by the method for producing the fatty acid ester of the present invention.

  According to the method and apparatus for producing a fatty acid ester of the present invention, surplus alcohol has been recovered from glycerin separated after the transesterification reaction through complicated steps such as distillation. It can collect | recover and can use for a new transesterification again, The alcohol amount used at the time of manufacture of fatty acid ester can be reduced significantly. Therefore, the production method and production apparatus for fatty acid esters of the present invention enable more effective use of resources than ever before.

  According to the fuel of the present invention, since it is composed of fatty acid esters with reduced impurities, it is possible to provide high-quality fuel, and it is possible to efficiently produce fatty acid esters by effectively using resources, thereby reducing manufacturing costs. Can do.

  Hereinafter, the manufacturing apparatus and manufacturing method of the fatty acid ester of the present invention will be described in detail with reference to the drawings. 1 and 2 are diagrams showing a schematic configuration of a fatty acid ester production apparatus according to the present invention.

(First embodiment)
As shown in FIG. 1, the fatty acid ester production apparatus 10 according to the first embodiment of the present invention includes a pretreatment means 11, a pretreatment liquid separation means 12, a transesterification reaction means 13, and a reaction liquid. The separation unit 14, the cleaning unit 15, and the filtering unit 16 are configured.

  This pretreatment means 11 is supplied with edible oil and / or waste edible oil as a raw material for the transesterification reaction, glycerin containing alcohol, and an alkaline substance, and performs a pretreatment step of mixing them. is there.

  The raw edible oil and / or waste edible oil includes vegetable oils composed of fatty acid and glycerin esters, such as rapeseed oil, palm oil, soybean oil, sesame oil, corn oil, safflower oil, etc. Examples include waste edible oil that is used and discarded, and may be a mixture of edible oil and waste edible oil. Here, it can be easily obtained from restaurants, food factories, general households, etc., and the price can be reduced, and the amount of edible oil discarded can be reduced, contributing to the solution of environmental problems. Since it is possible, it is preferable to use waste cooking oil.

  The glycerin containing alcohol is not limited as long as it contains an alcohol which is a raw material for the transesterification reaction. For example, the glycerin is separated after edible oil and / or waste edible oil and alcohol are transesterified. Glycerin.

  This glycerin is preferably used because it contains alcohol and can be used effectively for the reaction. The glycerin is preferably obtained by a separation operation during the previous transesterification reaction and stored. Glycerin may be used, or when continuously reacting, the separated glycerin may be used while circulating.

  The alcohol contained in the glycerin is an aliphatic alcohol used in the transesterification reaction, preferably a lower aliphatic alcohol having 1 to 4 carbon atoms, and particularly preferably methyl alcohol.

  Examples of the alkaline substance include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide, and alkali metal alkoxides such as sodium methylate and sodium ethylate, which are soluble in water. It is preferable to add it as an alkaline aqueous solution. At this time, a mixed solution to which glycerin containing substantially no water is further added can be used.

  By mixing these, the alcohol contained in glycerin is converted to methyl ester and transferred to an ester layer composed of edible oil and / or waste edible oil, and the alcohol is reused as a raw material for the transesterification reaction. be able to. That is, this operation makes it possible to effectively use resources such as recovering and reusing excess alcohol used in the transesterification reaction.

  Furthermore, according to this method, alcohol can be easily reused by mixing the reaction separation liquid (glycerin) after the transesterification reaction, and complicated operations and apparatuses such as distillation that have been conventionally performed are used. Compared with the alcohol recovery method, the alcohol can be reused with an extremely simple operation and apparatus configuration.

  Also, by using glycerin that does not substantially contain water, the water contained in the edible oil and / or waste edible oil is dissolved and extracted in the glycerin layer, and the water that inhibits the transesterification reaction is edible oil and / or waste. It can also be removed from the edible oil, and the alkaline substance converts the free fatty acid in the edible oil and / or waste edible oil into soap and removes it.

  For example, in glycerin containing alcohol, the catalyst used in the transesterification reaction remains, and sodium hydroxide is usually used as this catalyst. In this case, the by-product soap becomes a solidified sodium salt, and glycerin is taken in at room temperature to generate a large amount of solids, which requires special consideration for preventing solidification.

  As a method for preventing solidification, for example, the pretreatment means 11 and the next pretreatment liquid separation means 12 are heated to 40 to 80 ° C. by a heating facility, or a cleaning means for clogging is provided. Can be mentioned.

  Another means for preventing solidification is to use potassium hydroxide as the alkaline substance to be mixed in the pretreatment step. Potassium hydroxide produces a soap that is softer than sodium hydroxide, and produces a potassium salt soap to reduce the rate of solidification and obtain a soap glycerin mixture with excellent fluidity. Can be made easier.

  As a method for adding potassium to form a potassium salt, an aqueous solution of potassium hydroxide may be added to a mixture of edible oil and / or waste edible oil and glycerin, or a mixture previously mixed with glycerin and water. The liquid may be mixed with edible oil and / or waste edible oil. At this time, by adding and mixing glycerin substantially free of moisture, it is possible to remove moisture contained in the edible oil and / or waste edible oil in the pretreatment step.

  This addition of potassium hydroxide is preferably carried out so as to have a predetermined mass ratio with the remaining sodium hydroxide, and the amount of sodium hydroxide is 1 to 10 with respect to potassium hydroxide 1. preferable. The higher ratio of potassium hydroxide is preferable from the viewpoint of fluidity, but since the price is several times higher, it is preferable to set the above ratio in consideration of the economic aspect.

  When potassium hydroxide is prepared in advance as a mixed liquid of glycerin and water, the amount of glycerin to be added is preferably 1 to 10 parts by mass with respect to 1 part by mass of potassium hydroxide. In addition, it is preferable that 1 to 5 parts by mass of potassium hydroxide dissolving water is mixed per 1 part by mass of potassium hydroxide.

  By adding this mixture of potassium hydroxide, glycerin and water at a ratio of 0.1 to 10 parts by weight per 100 parts by weight of edible oil and / or waste edible oil, it is included in edible oil and / or waste edible oil. Neutralizes higher fatty acids, making it easy to separate as a soft potassium soap.

  The glycerin substantially free of moisture used at this time is an acidic substance added to the glycerin layer separated from the transesterification reaction liquid or pretreatment liquid described later to convert soap into fatty acid and salt, The lower layer (glycerin layer) from which the upper layer (ester layer) has been removed is distilled to remove alcohol, moisture, etc., and then further distilled.

  As described above, free fatty acids in edible oils and / or waste edible oils are removed as potassium soap, and moisture in edible oils and / or waste edible oils is removed by a short separation operation by moving to the glycerin layer. Can do. Here, the use of glycerin in the pretreatment step greatly contributes not only to the removal of moisture but also to the separation in a short time.

  For example, simply adding an aqueous potassium hydroxide solution required a long standing time (several hours or more) to separate the two layers, but in addition to this, mixing glycerin Thus, clear separation was possible in a very short time (within 1 hour), and the separation operability could be greatly improved.

  The liquid mixture (pretreatment liquid) obtained in such a pretreatment step is sent to the pretreatment liquid separation means 12, and the edible oil and / or waste edible oil layer is mainly the upper layer, and the soap-containing glycerin layer is the lower layer. A pretreatment liquid separation step is performed in which these are separated and separated by discharging them separately. Here, the edible oil and / or the waste edible oil layer is a raw material for the transesterification reaction, and is sent to the next transesterification reaction means 13. The separation of the pretreatment liquid here can be performed, for example, by the difference in specific gravity between the edible oil and / or the waste edible oil layer and the glycerin layer, and can be separated by standing or using a centrifuge. Alternatively, the pretreatment liquid separation means 12 may not be provided, and the pretreatment liquid may be sent to the next transesterification reaction means 13 without being separated.

  The transesterification reaction means 13 of the present invention adds an alcohol and a catalyst to the edible oil and / or the waste edible oil layer separated by the pretreatment separation means 12, so that the edible oil and / or the waste edible oil and the alcohol are mixed. The transesterification reaction is carried out to produce a fatty acid ester and glycerin.

  The transesterification reaction so far has been performed with the raw material alcohol at about 20 parts by mass with respect to 100 parts by mass of edible oil and / or waste edible oil. The theoretical amount at this time is, for example, that of waste edible oil In the case, it was about 12 to 14 parts by mass. That is, in actuality, about 1.5 times the theoretical amount of alcohol was used, and excess alcohol was used for the reaction.

  On the other hand, the transesterification reaction in the present invention is performed using edible oil and / or waste edible oil previously treated with a mixture of glycerin, potassium hydroxide and water, and at this time, the excess of the transesterification reaction Since about half of the alcohol can be recovered from the glycerin layer and reused, the amount of newly added alcohol can be reduced accordingly. In other words, it is possible to easily save resources accordingly.

  Furthermore, the amount of alkaline substance used as a catalyst is small because higher fatty acids have already been removed in the pretreatment step, and the amount of soap produced as a by-product in the transesterification reaction is also reduced. It becomes easy.

  The alcohol and catalyst added in the transesterification means 13 are as described above. That is, examples of the alcohol include aliphatic alcohols. For example, lower alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol are preferable, and methyl alcohol is preferable. Particularly preferred. Examples of the catalyst include alkaline substances such as alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide, and alkali metal alkoxides such as sodium methylate and sodium ethylate. Particularly preferred is sodium oxide.

  Thus, the reaction liquid obtained by the transesterification means 13 is subjected to a reaction liquid separation step in which the reaction liquid separation means 14 separates the fatty acid ester layer and the glycerin layer. In addition, what is necessary is just to isolate | separate this reaction liquid using the specific gravity difference of a fatty-acid-ester layer and a glycerol layer by operation similar to isolation | separation of a pre-processing liquid, for example. In the present invention, since the amount of soap produced as a by-product in the transesterification reaction is smaller than the conventional amount as described above, the glycerin layer can be easily extracted from the reaction solution after the transesterification reaction. Can be performed easily.

  The fatty acid ester layer thus obtained is sent to the washing means 15, where by-product soap and alkali dissolved in the fatty acid ester by washing with water according to a conventional method such as press-fitting washing water into the washing means 15 A cleaning step is performed to remove water-soluble impurities such as methanol.

  Furthermore, after neutralizing soap by adding an acidic substance, separation of free fatty acid, dehydration operation, etc., and finally performing a filtration step of removing impurities such as solids by filtration means 16 made of filter paper etc. as a product Useful fatty acid esters are obtained.

  The purified fatty acid ester obtained through the above steps can be used as it is as a useful diesel fuel or fuel oil additive.

(Second Embodiment)
As shown in FIG. 2, the fatty acid ester production apparatus 20 according to the second embodiment of the present invention includes a pretreatment unit 11, a pretreatment liquid separation unit 12, a transesterification reaction unit 13, and a reaction solution. The separation means 14, the cleaning means 15, the filtration means 16, the glycerin circulation means 21, the fatty acid separation means 22, and the glycerin evaporation means 23 are configured.

  In the second embodiment, the same components as those in the first embodiment are denoted by the same reference numerals, and description thereof will be omitted below. That is, the second embodiment is different from the first embodiment only in that a glycerin circulation unit 21, a fatty acid separation unit 22, and a glycerin evaporation unit 23 are additionally provided. By doing so, the glycerin separated by each separation means and other components can be processed in order to make effective use.

  The glycerin circulation means 21 performs a glycerin circulation process in which the glycerin layer separated in the reaction liquid separation means 14 is circulated and supplied to the pretreatment means 11 using a pump or the like. The glycerin circulated here contains alcohol added excessively in the transesterification reaction, and can be utilized as glycerin containing alcohol added in the pretreatment means 11 by circulating as it is. .

  The fatty acid separation means 22 adds an acid to the soap glycerin mixed liquid separated by the pretreatment liquid separation means 12, returns the soap contained in the mixed liquid to the fatty acid, and separates the organic layer composed of the fatty acid. A separation step is performed.

  The glycerin evaporating means 23 heats the glycerin layer remaining after the fatty acid is separated by the fatty acid separating means 22 under reduced pressure, thereby first distilling alcohol and water such as methanol and water, and then increasing the degree of vacuum to glycerin. Is evaporated, and a glycerin evaporation step is performed in which this is recovered as anhydrous glycerin. At this time, the glycerin evaporating means 23 includes a vacuum evaporator equipped with a heating kettle. First, after removing alcohol and water at 101 to 13 kPa and 70 to 100 ° C., the water is made 8 to 6 kPa and 205 to 215 ° C. It is preferred to recover glycerin.

  The anhydrous glycerin obtained here can be used as glycerin added together with potassium hydroxide and water in order to remove moisture contained in the edible oil and / or waste edible oil in the pretreatment step. In addition, it can be used for a dehydration operation performed after the fatty acid ester washing means 15.

  In this embodiment, not only the alcohol is effectively utilized but also the glycerin separated by the pretreatment liquid separation means 12 and the reaction liquid separation means 14 is further utilized to produce the fatty acid ester. Thus, it is possible to utilize the resources extremely effectively and to produce the fatty acid ester at a lower cost.

EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited to the following Example. The reaction rate of fatty acid methyl ester was measured by the following method.
Weigh about 150 grams of purified fatty acid methyl ester as a sample into a 300 mL flask. Next, this flask is attached to a distillation apparatus comprising a heating apparatus equipped with a mantle heater, a collection apparatus equipped with a water-cooled condenser tube, and a vacuum pump. The vacuum pump is started, the pressure is reduced to 3 to 5 mmHg with a mercury manometer, the flask is heated with a mantle heater, and distilled at a vapor layer temperature of 195 to 200 ° C. Receive the distillate in a separate flask, weigh it, and calculate the reaction rate using the following formula.
Reaction rate (%) = [weight of distillate / weight of purified fatty acid methyl ester] × 100

Comparative Example 1

  1,050 kg of used cooking oil (hereinafter referred to as waste cooking oil) collected from a restaurant or the like was charged into a 2,000 L reaction kettle with a stirring device equipped with a jacket heating device using steam. This was heated to about 50 ° C. with stirring. Next, 10 kg of a mixed solution of 15% by mass of potassium hydroxide, 30% by mass of water and 55% by mass of glycerin was added as a pretreatment agent, and after stirring for 30 minutes, the stirring was stopped and the mixture was allowed to stand for 1 hour. Thereafter, 60 kg of a liquid mainly composed of a lower layer potassium soap was extracted. To the remaining upper layer solution, 210 kg of methanol solution containing 10 kg of sodium hydroxide was added as a reaction solution, and the mixture was reacted for 1 hour with stirring while maintaining the temperature at 50 ° C.

  Stirring was stopped and the mixture was allowed to stand for 1 hour, and 230 kg of the glycerin layer was extracted from the lower layer. The glycerol layer had a methanol concentration of 11% by mass. This glycerin layer was stored for use in the next pretreatment. 100 L of water containing hydrochloric acid was added to the upper liquid of the transesterification reaction for washing, and the washing water was extracted from the lower part. After repeating this washing operation twice, a zinc sulfate aqueous solution was added to the upper layer liquid, and the remaining soap was converted into metal soap and precipitated. Next, anhydrous glycerin and acid clay were added and mixed with stirring, followed by filtration to obtain 950 kg of purified fatty acid methyl ester. The reaction rate of this purified fatty acid was 96.1%.

  In this case, the amount of one-pass methanol used was 200 kg per 950 kg of the fatty acid ester.

  1,050 kg of used cooking oil collected from a restaurant or the like was charged into a reaction kettle having the same configuration as that of Comparative Example 1. Next, 10 kg of a mixed solution of 230 kg of the glycerin layer stored in Comparative Example 1, 15% by mass of potassium hydroxide, 30% by mass of water, and 55% by mass of glycerin was added. After stirring for 30 minutes at a temperature of 50 ° C., the mixture was allowed to stand for 1 hour. 285 kg of a liquid mainly composed of glycerin was extracted from the lower layer. The methanol concentration of this liquid was 1.1%. Also, there was no problem with fluidity.

  Next, 183 kg of a methanol solution containing 8 kg of sodium hydroxide was added as a reaction solution to the upper layer solution, and the mixture was reacted for 1 hour while stirring at 50 ° C. Stirring was stopped and the mixture was allowed to stand for 1 hour, and 213 kg of the glycerin layer was extracted from the lower layer. The glycerol layer had a methanol concentration of 12%. This glycerin layer was subsequently stored for use in the next pretreatment. The upper liquid of the transesterification reaction was treated in the same manner as in Comparative Example 1 to obtain 950 kg of purified fatty acid methyl ester. The reaction rate of this purified fatty acid methyl ester was 96.0%.

  In this case, the amount of one-pass methanol used was 175 kg per 950 kg of the fatty acid ester.

  Compared with Comparative Example 1, the amount of methanol used could be reduced by 25 kg per 950 kg of fatty acid ester. This shows that it has decreased from 0.211 to 0.184 in terms of methanol basic unit.

  10 kg of the lower glycerin layer obtained by the separation of the pretreatment liquid in Example 1 was taken out and placed in a 20 L container with a stirrer. To this, 5 L of 10% hydrochloric acid aqueous solution was added to carry out a neutralization reaction to convert soap into fatty acid, the upper fatty acid layer was removed, and the lower glycerin and sodium chloride aqueous solution were charged into a vacuum evaporator equipped with a heating kettle. First, while gradually reducing the pressure from 101 kPa to 13 kPa, the temperature is heated from 70 ° C. to 100 ° C., and water containing 0.1 kg of methanol is first distilled, and then the degree of vacuum is increased to 8 kPa to 6 kPa. While gradually reducing the pressure, the temperature was heated from 205 ° C. to 215 ° C. to evaporate glycerin to obtain 6 kg of anhydrous glycerin.

  The obtained anhydrous glycerin was used in a pretreatment step by being mixed with waste edible oil together with potassium hydroxide and water.

  Waste cooking oil heated to 50 ° C. 100 kg / h, potassium hydroxide 15% by mass, glycerin 55% by mass, water 30% by mass 1 kg / h, glycerol layer separated after transesterification reaction at 23 kg / h, After mixing each in a pump, this mixed solution is fed into a 500 L tank maintained at a temperature of 50 ° C. by a jacket heating device at an angle tangential to the wall surface. It was supplied while producing a swirling flow in the inside.

  The soap solution was continuously extracted from the lower part of the tank at 21 kg / hour, and the waste cooking oil after the pretreatment was continuously extracted from the upper part of the tank at 103 kg / hour. Subsequently, the pre-treated waste edible oil was mixed at 103 kg / h and methanol solution containing 5% by weight of sodium hydroxide at 18 kg / h, and then mixed into a tubular reactor having an inner diameter of 25 mm and a length of 122 m. did. The transesterification reaction was carried out while maintaining the tubular reactor at a temperature of 50 ° C. with a jacket heating device, and the ester layer and the glycerin layer were separated at the outlet of the tubular reactor by a separator based on the difference in specific gravity.

  The upper ester layer was withdrawn at 97 kg / h for the washing means, and the lower glycerin layer was withdrawn at 24 kg / h, of which 23 kg was continuously returned to the first tubular reactor by the circulation means, and the remainder was used for the production of anhydrous glycerin. Next, after the ester layer is guided to the cleaning means and washed, an aqueous solution of zinc sulfate is added, and anhydrous glycerin and acidic clay are added, followed by filtration with a continuous filtration device, and 95 kg of purified fatty acid ester, which is the product, per hour. Obtained. At this time, the basic unit of methanol per product was 0.18. The reaction rate of this purified fatty acid methyl ester was 96.1%.

It is the figure which represented typically the manufacturing apparatus of the fatty acid ester of this invention. It is the figure which represented typically the manufacturing apparatus of the fatty acid ester of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Fatty acid ester manufacturing apparatus, 11 ... Pretreatment means, 12 ... Pretreatment liquid separation means, 13 ... Transesterification reaction means, 14 ... Reaction liquid separation means, 15 ... Washing means, 16 ... Filtration means, 20 ... Fatty acid ester production Apparatus, 21 ... circulation means, 22 ... fatty acid separation means, 23 ... glycerin evaporation means

Claims (13)

A pretreatment step of mixing edible oil and / or waste edible oil with glycerin containing alcohol and an alkaline substance;
The edible oil and / or waste edible oil obtained in the pretreatment step is mixed with alcohol in the presence of an alkali catalyst to undergo a transesterification reaction to produce a fatty acid ester and glycerin;
A reaction liquid separation step for separating the reaction liquid after the transesterification reaction into a fatty acid ester layer and a glycerin layer;
A method for producing a fatty acid ester and glycerin, comprising:   The fatty acid ester and glycerin according to claim 1, wherein a pretreatment liquid separation step of separating the pretreatment liquid obtained in the pretreatment step into an edible oil and / or a waste edible oil layer and a glycerin layer is performed. Production method.   The method for producing a fatty acid ester and glycerin according to claim 1 or 2, wherein the glycerin used in the pretreatment step is glycerin obtained in the reaction liquid separation step.   As the glycerin used in the pretreatment step, an anhydrous substance obtained by adding an acidic substance to the glycerin obtained in the reaction liquid separation step or the pretreatment liquid separation step and then distilling the obtained glycerin layer. The method for producing a fatty acid ester and glycerin according to any one of claims 1 to 3, comprising glycerin.   The method for producing a fatty acid ester and glycerol according to any one of claims 1 to 4, wherein the alkaline substance used in the pretreatment step is potassium hydroxide.   In the pretreatment step, the alkaline substance is mixed as an aqueous alkaline solution, and the mass ratio of glycerin, alkaline substance and water is glycerin 1 to 10 and water 1 to 5 with respect to the alkaline substance 1. A method for producing a fatty acid ester and glycerin according to any one of claims 1 to 5.   The fatty acid according to claim 6, wherein 0.1 to 10 parts by mass of a mixed solution of glycerin and an aqueous alkali solution used in the pretreatment step is mixed with 100 parts by mass of the edible oil and / or waste edible oil. Method for producing ester and glycerin.   The alkali catalyst used in the transesterification reaction step is sodium hydroxide, and in the pretreatment step, the mass ratio with potassium hydroxide is 1 to 10 with respect to potassium hydroxide 1, The method for producing a fatty acid ester and glycerin according to any one of claims 1 to 7. To the glycerin separated in the pretreatment liquid separation step, an acid is added, mixed to produce a fatty acid, and a fatty acid separation step of separating the fatty acid and glycerin;
Glycerol evaporation step of fractionating anhydrous glycerol by further reducing the pressure after removing alcohol and water under reduced pressure after the glycerol separated by the fatty acid separation step;
The method for producing a fatty acid ester and glycerin according to any one of claims 1 to 8, wherein: Pretreatment means for mixing edible oil and / or waste edible oil with glycerin containing alcohol and an alkaline substance;
Pretreatment liquid separating means for separating the pretreatment liquid obtained by the pretreatment means into an edible oil and / or a waste edible oil layer and a glycerin layer;
The edible oil and / or waste edible oil obtained by the pretreatment liquid separating means is mixed with alcohol in the presence of an alkali catalyst to perform a transesterification reaction, thereby generating a fatty acid ester and glycerin,
A reaction liquid separating means for separating the reaction liquid after the transesterification reaction into a fatty acid ester layer and a glycerin layer;
An apparatus for producing a fatty acid ester and glycerin, comprising:   The apparatus for producing a fatty acid ester and glycerin according to claim 10, further comprising a glycerin circulation unit that uses the glycerin separated by the reaction liquid separating unit as glycerin to be supplied to the pretreatment unit. Fatty acid separation means for adding and mixing an acid to glycerol separated by the pretreatment liquid separation means to produce a fatty acid and separating the fatty acid and glycerin;
Glycerol obtained by the fatty acid separation means, after removing alcohol and water under reduced pressure, glycerin evaporation means for further reducing the pressure and fractionating anhydrous glycerol,
The apparatus for producing a fatty acid ester and glycerin according to claim 10 or 11, characterized by comprising:   The fuel containing the fatty acid ester obtained by the manufacturing method of the fatty acid ester and glycerol of any one of Claims 1 thru | or 9.

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