JP2010195938A - Method for producing fatty acid ester and apparatus for producing fatty acid ester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method etc., for producing fatty acid ester more easily and more economically. <P>SOLUTION: The method for producing a fatty acid ester has a production step of producing the fatty acid ester by introducing oils and fats and alcohols into a reaction column 13 filled with an anion exchange resin as a catalyst, thereby allowing a transesterification reaction; a separation step of separating the produced fatty acid ester from by-products through a separation vessel 14; a transfer step of transferring the reaction column 13, removing the anion exchange resin from the plurality of the reaction columns 13, and filling a regeneration column in which a regeneration processing of the anion exchange resin; a regeneration step of carrying out the regeneration processing of the anion exchange resin is carried out in the regeneration column different from the reaction column 13; a return process of removing the regenerated anion exchange resin from the regeneration column, filling the reaction column 13 with the regenerated anion exchange resin, and returning the reaction column 13. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a fatty acid ester, and more particularly to a method for producing a fatty acid ester by an ester exchange reaction between oils and fats and alcohols.

Fatty acid esters synthesized by transesterification of fats and alcohols are attracting attention as biodiesel fuels that can be regenerated with carbon neutral (zero increase in carbon dioxide on the earth). This fuel can be used as it is in any type of diesel engine, and is more easily biodegradable than conventional petroleum-based diesel fuel (light oil). It has high lubricity, carbon monoxide, hydrocarbons, and particulate matter. Etc., and the emission gas does not contain sulfur oxides or sulfates.
In addition, since it can be synthesized from waste cooking oil, it is also attracting attention as an environment-friendly waste effective utilization technology.

  Here, in the conventional production process, a soaking alkali catalyst such as potassium hydroxide or sodium hydroxide is used to promote the transesterification reaction. In the fatty acid ester obtained by the reaction, a saponified fatty acid (soap) and an alkali component as a catalyst are mixed. Since this is unsuitable as a biodiesel fuel, it is necessary to perform purification such as water washing. In addition, a large amount of alkali component is also mixed in glycerin, which is a by-product, which is a problem in reuse. Therefore, a method for producing a fatty acid ester without using a soaking alkali catalyst is desired.

  Here, Patent Document 1 discloses a method for producing a fatty acid ester by a transesterification reaction between an oil and fat and an alcohol, using an anion exchange resin as a catalyst, and the molar ratio of the oil and fat to the alcohol is 1/30. A method for producing a fatty acid ester characterized in that it is ˜1 / 1 is disclosed.

JP 2006-104316 A

  However, in the method of producing a fatty acid ester using an anion exchange resin as a catalyst, the anion exchange resin deteriorates due to deactivation or the like during the reaction, and thus a regeneration treatment for regeneration is necessary. Conventionally, this regeneration treatment is performed using a reactor for performing the transesterification reaction as it is. Therefore, it is necessary to provide a chemical dispersion mechanism used for regeneration treatment, a waste liquid discharge mechanism, and the like, and the arrangement of the reactor and the piping around the reactor become complicated. Therefore, there is a problem that the plant itself is uneconomical and the operation is complicated.

The present invention has been made in view of the above-described problems of conventional techniques.
That is, an object of the present invention is to provide a production system in which a fatty acid ester is produced by mixing fats and oils, alcohols and an anion exchanger as a catalyst, and an anion exchanger having a reduced catalytic function due to deactivation or the like in this reaction. By dividing the regeneration system into a regeneration system, an object is to provide a method for producing a fatty acid ester more easily and more economically.

  Another object is to simplify the structure of the reactor used to produce fatty acid esters by mixing oils and fats, alcohols, and anion exchangers as catalysts, making it easier and more economical. It is intended to provide an apparatus for producing a fatty acid ester.

  Thus, the method for producing a fatty acid ester of the present invention is a method for producing a fatty acid ester by using an anion exchanger as a catalyst to produce a fatty acid ester by a transesterification reaction between fats and alcohols. A production step for producing a fatty acid ester by introducing it into a reactor filled with an exchanger, a separation step for separating the produced fatty acid ester from a by-product, an anion exchanger from a plurality of reactors by transferring the reactor The transfer step for taking out the regenerator and filling it into the regenerator, the regenerative step for regenerating the anion exchanger in a regenerator different from the reactor, and the regenerated anion exchanger from the regenerator for the reaction And a returning step of filling and returning to the vessel.

Here, the reactor is detachable, and it is preferable to transfer and return the reactor while the anion exchanger is filled in the reactor.
The regeneration step is preferably performed by eluting the fatty acid adsorbed on the anion exchanger and hydroxylating the anion exchanger.
Furthermore, before the production step, a cation exchanger may be used as a catalyst, and a fatty acid ester may be produced by an esterification reaction of free fatty acid contained in fats and oils to further remove the free fatty acid. preferable.

  The fatty acid ester production apparatus of the present invention is a fatty acid ester production apparatus for producing a fatty acid ester by an ester exchange reaction between an oil and fat and an alcohol using an anion exchanger as a catalyst. A detachable reactor for mixing the exchanger to produce a fatty acid ester, a separator for separating the produced fatty acid ester from a by-product, a transfer means for transferring the reactor to a regenerator for regeneration treatment, and anion exchange It is characterized by having a regenerator different from the reactor for regenerating the body, and a return means for filling the regenerated anion exchanger into the reactor and returning it.

Here, it is preferable to further have a remover that removes free fatty acids contained in fats and oils by using a cation exchanger.
The transfer means includes means for sending the anion exchanger to the regenerator after storing the anion exchanger taken out from the plurality of reactors, and the return means is for returning the regenerated anion exchanger from the regenerator. Preferably it includes means for sending it to the retrieval reservoir.

  According to the present invention, fatty acid esters can be produced more easily and more economically.

  The best mode for carrying out the present invention (hereinafter, an embodiment of the present invention) will be described in detail below. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary. Further, the drawings to be used are for explaining the present embodiment and do not represent the actual size.

(Oils and fats)
The fats and oils used in the present embodiment are not particularly limited, and may be natural fats and oils, synthetic fats and oils, or a mixture thereof.
For example, soybean oil, palm oil, palm oil, palm kernel oil, corn oil, peanut oil, sunflower oil, olive oil, safflower oil, coconut oil, oak oil, almond oil, black walnut oil, apricot oil, cocoa butter oil , Dairy oil, safflower oil, china oil, flaxseed oil, cottonseed oil, rapeseed oil, giraffe oil, castor oil, cottonseed stearin, sesame oil, coffee bean oil, camellia oil, rice bran oil, etc .; lard oil, chicken oil , Butter oil, cod liver oil, deer oil, dolphin oil, sardine oil, mackerel oil, horse fat, pork fat, bone oil, sheep fat, cow leg oil, murine dolphin oil, shark oil, sperm whale oil, whale oil, beef tallow, Animal fats and oils such as beef bone fat; waste cooking oil discarded from restaurants, food factories, general households, etc.
Or these oils and fats alone or mixed, those containing diglycerides and monoglycerides, synthesized triglycerides, synthetic triglycerides containing monoglycerides and diglycerides, and some of these oils and fats are treated by oxidation, reduction, etc. Modified oils and fats may be used. Furthermore, processed oils and fats mainly composed of these oils and fats can also be used.

(Alcohols)
Although alcohols used in this embodiment are not particularly limited, it is preferable to use an alcohol having a saturated linear or branched hydrocarbon skeleton having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. .
For example, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol and the like can be mentioned. These alcohols can be used alone or in admixture of two or more. However, it is preferable to use methanol or ethanol from the viewpoint of availability and availability of the obtained fatty acid ester. Of these, methanol is particularly preferred from the viewpoint of economy.
In the present embodiment, alcohols act as reaction substrates in transesterification reactions with fats and oils, and also have a solvent action for adjusting the dilution and viscosity of fats and oils.

(Anion exchanger)
As the anion exchanger used as a catalyst in the present embodiment, an anion exchange resin, an anion exchange membrane and the like can be used, and among these, an anion exchange resin is preferable. The anion exchange resin can be classified into a strong basic anion exchange resin, a weak basic anion exchange resin, and the like, but a strong basic anion exchange resin is more preferable. Further, when the anion exchange resin is classified according to the degree of crosslinking or porosity, a gel type, a porous type, a high porous type and the like can be mentioned, and a porous type and a high porous type are more preferable.
Specifically, for example, Diaion PA-306, Diaion PA-306S, Diaion PA-308, Diaion HPA-25 manufactured by Mitsubishi Chemical Corporation; Dowex 1-X2 manufactured by Dow Chemical Japan Co., Ltd. Amberlite IRA-45, Amberlite IRA-94, etc. manufactured by Organo Corporation can be used.

Since the above-mentioned commercially available anion exchange resins are usually in the Cl form, in this embodiment, they are substituted with OH groups and used in the OH form. This substitution method can be performed, for example, by filling the column with an anion exchange resin before treatment and passing a 0.5 mol / dm ³ to 2 mol / dm ³ aqueous NaOH solution as a substitution agent. In this case, the liquid passing rate is preferably about 2 ml to 10 ml-NaOH / min per 1 ml of the anion exchange resin. Moreover, it is preferable that the liquid flow rate is 5 to 20 ml per 1 ml of anion exchange resin. After the substitution is completed, the resin is taken out from the column and sufficiently washed with distilled water so that the substitution agent does not remain.

(Cation exchanger)
As the cation exchanger used for removing free fatty acids contained in fats and oils in the present embodiment, a cation exchange resin, a cation exchange membrane or the like can be used, and among them, a cation exchange resin is preferable. The cation exchange resin can be classified into a strong acid cation exchange resin, a weak acid cation exchange resin, and the like, but a strong acid cation exchange resin is more preferable. Examples of the strongly acidic cation exchange resin include acidic ion exchange resins having a sulfone group. In addition, when the cation exchange resin used in the present embodiment is classified by the degree of crosslinking or porosity, a gel type, a porous type, a high porous type, and the like can be mentioned, and any of them can be used.
Specifically, Diaion PK208LH, Diaion PK216LH, Diaion PK228LH manufactured by Mitsubishi Chemical Corporation, Amberlist 15DRY, Amberlist 16DRY, Amberlist 31DRY, etc. manufactured by Organo Corporation can be used.

  Next, an example of an apparatus for producing a fatty acid ester to which the present embodiment is applied will be specifically described with reference to the drawings. In the present embodiment, the fatty acid ester production apparatus is broadly classified into a production system that produces a fatty acid ester and a regeneration system that regenerates an anion exchanger having a reduced catalytic function due to deactivation or the like.

FIG. 1 is a diagram illustrating an example of a generation system according to the present embodiment.
The fatty acid ester production apparatus 10 as a production system shown in FIG. 1 removes a fat storage tank 11a for storing fats and oils, a methanol storage tank 11b for storing methanol as alcohols, and free fatty acids contained in the fats and oils. Free fatty acid removal column 12 as a remover filled with a cation exchange resin, and fats and methanol from which free fatty acids have been removed are introduced and methanol is mixed with the fats, methanol, and anion exchange resin, and subjected to a transesterification reaction. Reaction column 13 as a reactor for producing fatty acid ester, separation tank 14 as a separator for stationary separation of produced fatty acid ester and by-product glycerin, and fatty acid for storing fatty acid ester separated from glycerin It has an ester storage tank 15 and a glycerin storage tank 16 for storing by-product glycerin. .

And the fats and oils storage tank 11a, the methanol storage tank 11b, and the free fatty-acid removal column 12 are connected by piping through the supply pumps of fat and methanol. Moreover, the free fatty acid removal column 12, the reaction column 13, and the separation tank 14 are connected in series by piping or the like. Further, the separation tank 14, the fatty acid ester storage tank 15, and the glycerin storage tank 16 are connected by a pipe. As piping, what consists of materials, such as Teflon (trademark), can be used.
In addition, the free fatty acid removal column 12 and the reaction column 13 are respectively provided with heaters 17a and 17b for warming each column to promote the reaction and to keep each column warm.

  Hereinafter, the process is demonstrated about the production | generation system which produces | generates fatty acid ester by the fatty acid ester production | generation apparatus 10 comprised in this way.

(Removal process)
In the present embodiment, an anion exchange resin is used as a catalyst, and free fatty acids contained in the fats and oils are removed by a cation exchange resin as a pretreatment in a production step of producing a fatty acid ester by an ester exchange reaction between the fats and methanol. It is preferable to provide a removal step. That is, free fatty acids are removed by producing fatty acid esters by esterification reaction of free fatty acids contained in fats and oils with methanol using a cation exchange resin as a catalyst.
In the present embodiment, this free fatty acid does not cause a saponification reaction and does not become an impurity in the transesterification reaction in the next production step. Therefore, although the removal process which removes free fatty acid with a cation exchange resin is not essential, the yield of fatty acid ester will fall. Moreover, when waste cooking oil etc. are used as fats and oils, it is easy to produce fluctuation | variation in the quantity of the free fatty acid contained in it. Therefore, it is effective to provide a removal step from the viewpoint of reducing the fluctuation and producing a fatty acid ester having stable quality.

  As a specific procedure, first, oil and fat and methanol are sent from the oil and fat storage tank 11 a and the methanol storage tank 11 b by a pump (not shown) and introduced into the free fatty acid removal column 12. The free fatty acid removal column 12 is filled with a cation exchange resin in advance, and the above-described reaction occurs when this cation exchange resin is mixed with fats and oils and methanol. As a result, free fatty acids contained in the fats and oils are removed. Moreover, the inside of the free fatty acid removal column 12 is heated to an appropriate temperature by the heater 17a, and the reaction is efficiently performed. The temperature in the free fatty acid removal column 12 can be set to 60 ° C., for example.

(Generation process)
Next, the fats and oils from which free fatty acids have been removed and methanol are introduced into the reaction column 13. For introduction into the reaction column 13, a pump or the like may be used, but it can also be introduced into the reaction column 13 by the residual pressure from the free fatty acid removal column 12.
The reaction column 13 is filled with an anion exchange resin in advance, and by introducing fats and oils and methanol into the reaction column 13 filled with the anion exchange resin, an ester exchange reaction occurs and a fatty acid ester is generated. In addition, glycerin is produced as a by-product.
The reaction formula of the transesterification reaction generated here is as follows. Here, triglyceride is used as an example for fats and oils, and methanol is used as a general alcohol.

Further, the transesterification reaction is heated to an appropriate temperature by the heater 17b attached to the reaction column 13, and the reaction is efficiently performed. The reaction temperature is preferably 30 ° C to 90 ° C, more preferably 40 ° C to 60 ° C.
The reaction pressure is preferably 0.05 MPa to 10 MPa, more preferably 0.05 MPa to 1 MPa, but it is usually performed under atmospheric pressure.

  Moreover, since this reaction is a reversible reaction, an equilibrium yield exists. Therefore, in the fatty acid ester phase containing the fatty acid ester, unreacted triglyceride, diglyceride and monoglyceride as intermediate products often remain in addition to the fatty acid ester. From the viewpoint of diesel engine fuel, which is the use of fatty acid esters, these other products induce clogging of engine system filters and cause engine trouble. In order to prevent this, it is preferable to add alcohol as a raw material in excess of the stoichiometric ratio (for example, 5 molar equivalent to 10 molar equivalent of triglyceride).

In addition, the reaction column 13 of the fatty acid ester production | generation apparatus 10 shown in FIG. For example, by providing a plurality of reaction columns 13 in series, a transesterification reaction can be performed in a stepwise manner, and a high-purity fatty acid ester is easily generated.
Further, in the above-described example, the heaters 17a and 17b are used to warm and keep the free fatty acid removal column 12 and the reaction column 13, but the heaters 17a and 17b are limited to those having a warming function and a warming function. It is not a thing. For example, a method of using a jacket with a free fatty acid removal column 12 or a reaction column 13 and heating it with hot water or steam can be employed.

(Separation process)
After the transesterification reaction, the produced fatty acid ester and glycerin are sent to the separation tank 14. For introduction into these separation tanks 14, a pump or the like may be used, but they may be introduced into the separation tank 14 by residual pressure from the reaction column 13.
Separation apparatus such as a centrifugal separator may be used separately for separation of fatty acid ester and glycerin, but fatty acid ester and glycerin have a difference in specific gravity, and normally, when left standing after completion of the reaction, they are separated into two layers by gravity. Therefore, the fatty acid ester and glycerin can be separated by standing in the separation tank 14.
In this embodiment, since the specific gravity of fatty acid ester is smaller than that of glycerin, fatty acid ester is an upper layer and glycerin is a lower layer and separated.

  Then, after the fatty acid ester and glycerin are sufficiently separated, the fatty acid ester is sent to the fatty acid ester storage tank 15, and the glycerin is sent to the glycerin storage tank 16 and stored therein.

  In addition, in the fatty acid ester production | generation apparatus 10 mentioned above, in order to remove the solid content contained in fats and oils, you may provide the filter (not shown) in front of the free fatty acid removal column 12 not shown. Further, a filter (not shown) may be similarly provided after the reaction column 13 in order to remove the crushed cation exchange resin or anion exchange resin.

  Here, the function of the anion exchange resin packed in the above-described reaction column 13 as a catalyst decreases due to deactivation or the like during the reaction. Therefore, it is necessary to regenerate the anion exchange resin having a reduced catalytic function. In the present embodiment, the regeneration of the anion exchange resin having a lowered catalyst function is performed by a regeneration system described below.

FIG. 2 is a diagram illustrating an example of a reproduction system according to the present embodiment.
An anion exchange resin regeneration device 20 as a regeneration system shown in FIG. 2 stores an anion exchange resin having a reduced catalyst function due to deactivation or the like and stores an anion exchange resin regenerated and stores the regenerated anion exchange resin 21. And a regeneration column 22 as a regenerator for regenerating an anion exchange resin having a reduced catalytic function, and an acid solution storage tank for storing an acid solution and an alkaline solution which are chemicals for regenerating the anion exchange resin having a decreased catalytic function 23a and an alkaline solution storage tank 23b, an acid waste liquid tank 24a for storing an acid solution which has become a waste liquid after being used to regenerate the anion exchange resin, and an alkaline waste liquid tank for storing an alkaline solution which has also become a waste liquid 24b, stored in an anion exchange resin storage tank 21 and an anion exchange resin storage tank 25 for storing clean water for washing the regenerated anion exchange resin Is catalytic function is provided with a water ejector 26 as means for sending the anion exchange resin reservoir 21 takes out the anion exchange resin was regenerated a means for sending to the regeneration column 22 anion exchange resin was reduced from the regeneration column 22. Here, the regeneration column 22 is different from the reaction column 13 (see FIG. 1).

  The anion exchange resin storage tank 21 and the regeneration column 22 are connected by a pipe via a water ejector 26. Similarly, the acid solution storage tank 23a, the alkaline solution storage tank 23b, the clean water storage tank 25, and the regeneration column 22 are connected to each other, and the regeneration column 22, the acid waste liquid tank 24a, and the alkaline waste liquid tank 24b are connected by piping. As piping, what consists of materials, such as a polyvinyl chloride, can be used.

  Hereinafter, a process of regenerating an anion exchange resin having a reduced catalyst function due to deactivation or the like by the anion exchange resin regenerating apparatus 20 configured as described above will be described.

(Transfer process)
First, the reaction column 13 containing the anion exchange resin having a lowered catalyst function is removed while being filled with the anion exchange resin. The reaction column 13 is detachable and is a so-called cartridge type. Then, the anion exchange resin having a lowered catalytic function can be transferred while being packed in the reaction column 13. Actually, the transfer is performed to a place where the anion exchange resin regenerator 20 is located.
After the reaction column 13 filled with the anion exchange resin having a reduced catalytic function is transferred to a place where the anion exchange resin regenerator 20 is located, the anion exchange resin having a reduced catalytic function is taken out of the reaction column 13 and once an anion exchange resin is obtained. It is stored in the storage tank 21. Here, the anion exchange resin storage tank 21 has a size capable of taking out and storing the anion exchange resin from the plurality of reaction columns 13.
Next, the water ejector 26 sends the anion exchange resin having a reduced catalytic function stored in the anion exchange resin storage tank 21 to the regeneration column 22 and transfers it to the regeneration column 22 for filling. Here, the regeneration column 22 has a sufficient size to be filled with the anion exchange resins taken out from the plurality of reaction columns 13, and a large number of the anion exchange resins can be regenerated at a time.

(Regeneration process)
Next, a predetermined acid solution is supplied into the regeneration column 22 from the acid solution storage tank 23a using a pump or the like (not shown). In this embodiment, an aqueous hydrochloric acid solution is used as the acid solution. As a result, the fatty acid adsorbed on the anion exchange resin having a reduced catalytic function can be eluted. At this time, the exchange group of the anion exchange resin is substituted with a chlorine group to form a chlorine form. After the acid treatment of the anion exchange resin in this manner, the used aqueous hydrochloric acid solution is withdrawn from the lower part of the regeneration column 22 as an acid waste liquid and sent to the acid waste liquid tank 24a.

Next, a predetermined alkaline solution is supplied into the regeneration column 22 from the alkaline solution storage tank 23b using a pump or the like (not shown). In this embodiment, an aqueous sodium hydroxide solution is used as the alkaline solution. As a result, the anion exchange resin is hydroxylated, and the chlorine group bonded as an exchange group is substituted with a hydroxyl group to be in the hydroxy form. After the alkali treatment of the anion exchange resin is performed in this way, the used aqueous sodium hydroxide solution is withdrawn from the lower portion of the regeneration column 22 as an alkaline waste liquid and sent to the alkaline waste liquid tank 24b.
Since the regeneration column 22 uses an acid solution or an alkali solution in this manner, it is preferable to use a steel plate having a rubber lining on the inner surface.

  Then, clean water is supplied from the clean water storage tank 25 into the regeneration column 22 using a pump or the like (not shown). As a result, the aforementioned acid or alkali solution can be diluted to a predetermined concentration and washed to remove the aqueous sodium hydroxide solution remaining in the anion exchange resin.

  The anion exchange resin having a reduced catalyst function can be regenerated by the above steps. Since this regeneration step can be performed with a batch size larger than the amount of anion exchange resin packed in the reaction column 13, the anion exchange resin can be more efficiently regenerated.

(Return process)
Then, the regenerated anion exchange resin is sent from the regeneration column 22 to the anion exchange resin storage tank 21 and stored by the water ejector 26 described above. The anion exchange resin storage tank 21 is provided with a mesh-like filter cloth for separating the anion exchange resin and water, and has a structure capable of draining water by opening a valve (not shown) at the bottom of the tank. . After the anion exchange resin is received in the anion exchange resin storage tank, the valve described above is opened and left for a sufficient period of time. Then, the regenerated anion exchange resin in a dry state is filled in the reaction column 13 again. At this time, when the reaction column 13 is set to a negative pressure by a vacuum generator (not shown) or the like, the anion exchange resin is easily sucked into the reactor by riding on the air flow generated there, and the anion exchange resin uses water for movement. Instead, the reaction column 13 is filled in a dry state. A mesh-like filter cloth that does not allow anion exchange resin to pass is provided between the vacuum generator and the reaction column 13.

  Then, the regenerated anion exchange resin is returned to the fatty acid ester generator 10 (see FIG. 1) where the fatty acid ester is generated while being packed in the reaction column 13, and is attached to the fatty acid ester generator 10 again.

  In this way, by transferring the fatty acid ester generator 10 to the anion exchange resin regenerator 20 and returning the anion exchange resin regenerator 20 to the fatty acid ester generator 10 while the reaction column 13 is filled with the anion exchange resin. Thus, the anion exchange resin can be transported more easily and safely.

  Moreover, it is not necessary to attach the fatty acid ester production | generation apparatus 10 and the anion exchange resin regeneration apparatus 20 to another system, and to attach the fatty acid ester production | generation apparatus 10 and to install the anion exchange resin reproduction | regeneration apparatus 20 in the same place. Therefore, it is difficult to be restricted by the place where the fatty acid ester generator 10 is installed. That is, the fatty acid ester can be produced in a narrow place or a place where it is difficult to obtain, handle, or treat the waste solution of an acid solution or an alkali solution.

  Furthermore, since a large amount of anion exchange resin can be regenerated together with the anion exchange resin regeneration device 20, loss of chemical solutions such as acid solution and alkali solution tends to be reduced. Furthermore, since the number of reproduction processes can be reduced, labor can be saved easily.

  Furthermore, the structure of the reaction column 13 can be simplified as compared with the conventional case where the reaction column 13 and the regeneration column 22 are combined. That is, it is not necessary to provide the reaction column 13 with a supply port for a chemical solution such as an acid solution or an alkali solution. In addition, it is necessary to introduce an acid solution or an alkali solution into the reaction column 13 for regeneration, and it is necessary to use a rubber-lined inner surface to prevent corrosion due to the acid solution or the alkali solution. In the embodiment, it is unnecessary. That is, a normal stainless steel column having no rubber lining on the inner surface can be used as the reaction column 13. Moreover, since the driving operation is simplified, the skill of the operator is not necessarily required.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited by these Examples, unless the summary is exceeded.

[Generator]
In this example, the fatty acid ester production apparatus 10 shown in FIG. 1 was used as the production system.
And, using waste cooking oil as fats and oils and methanol as alcohols, adjusting the molar ratio of waste cooking oil / methanol to 1 / 6.3, the fats and oils storage tank 11a and the methanol storage tank 11b Introduction into the free fatty acid removal column 12 was performed. Immediately before being introduced into the free fatty acid removal column 12, the solid content contained in the waste cooking oil was removed through a spool filter having a filtration accuracy of 3 μm.

  Next, the free fatty acid removal column 12 filled with Diaion PK208LH manufactured by Mitsubishi Chemical Corporation, which is a cation exchange resin, was passed through to remove the free fatty acid in the waste cooking oil by converting it to a fatty acid ester by an esterification reaction with methanol. At this time, the reaction was performed under atmospheric pressure, and the temperature in the free fatty acid removal column 12 was set to 60 ° C. by the heater 17a.

  Next, the exchange group of Diaion PA-306S manufactured by Mitsubishi Chemical Corporation, which is an anion exchange resin, is replaced with an OH group, and transesterification of waste cooking oil and methanol is performed using the anion exchange resin as a catalyst in the filled reaction column 13. Reacted. As a result, fatty acid ester and glycerin were produced. At this time, the reaction was performed under atmospheric pressure, and the temperature in the reaction column 13 was adjusted to 50 ° C. by the heater 17b.

  Next, the produced fatty acid ester and glycerin were introduced into the separation tank 14 and allowed to stand to separate the fatty acid ester and glycerin. After separation, the fatty acid ester was sent to the fatty acid ester storage tank 15, and the glycerin was sent to the glycerin storage tank 16 for storage.

[Reproduction system]
In this example, the anion exchange resin regeneration apparatus 20 shown in FIG. 2 was used as the regeneration system.
First, the reaction column 13 (see FIG. 1) is removed from the fatty acid ester generator 10 (see FIG. 1) while being filled with the anion exchange resin whose catalytic function has been lowered due to deactivation, and moved to a place where the anion exchange resin regenerator 20 is located. went.

Then, the anion exchange resin having a reduced catalytic function was taken out from the reaction column 13 and stored in the anion exchange resin storage tank 21.
Next, using a water ejector 26, an anion exchange resin having a reduced catalytic function was introduced into the regeneration column 22. In the present embodiment, an amount four times the amount of the anion exchange resin with reduced catalytic function packed in the reaction column 13 is introduced into the regeneration column 22.

Next, 5% hydrochloric acid aqueous solution from the acid solution storage tank 23a and 4% sodium hydroxide aqueous solution from the alkaline solution storage tank 23b are sequentially supplied into the regeneration column 22 and passed through to regenerate the anion exchange resin. Went. The used aqueous hydrochloric acid solution was sent to the acid waste liquid tank 24a, and the used sodium hydroxide aqueous solution was sent to the alkaline waste liquid tank 24b for storage.
Clean water was supplied from the clean water storage tank 25 into the regeneration column 22 for dilution of the hydrochloric acid aqueous solution and the sodium hydroxide aqueous solution, and the regenerated anion exchange resin was washed. The above reaction in the regeneration column 22 was carried out at room temperature under atmospheric pressure.

  After washing, the regenerated anion exchange resin was returned to the anion exchange resin storage tank 21 and stored again using the water ejector 26.

  Then, the regenerated anion exchange resin is again sent from the anion exchange resin storage tank 21 to the reaction column by an anion exchange resin drying operation in the anion exchange resin storage tank 21 as described above and pneumatic transport means such as a vacuum generator. 13 and moved to the fatty acid ester generator 10 while being packed in the reaction column 13. And it attached to the fatty acid ester production | generation apparatus 10 again. Using this regenerated anion exchange resin, it was confirmed that when the transesterification reaction between fats and oils and methanol was performed in the reaction column 13, it acted as a catalyst again to produce a fatty acid ester.

It is a figure which shows an example of the production | generation system by this Embodiment. It is a figure which shows an example of the reproduction | regeneration system by this Embodiment.

DESCRIPTION OF SYMBOLS 10 ... Fatty acid ester production | generation apparatus, 12 ... Free fatty acid removal column, 13 ... Reaction column, 14 ... Separation tank, 20 ... Anion exchange resin regeneration apparatus, 21 ... Anion exchange resin storage tank, 22 ... Regeneration column, 26 ... Water ejector

Claims (7)

A method for producing a fatty acid ester using an anion exchanger as a catalyst and producing a fatty acid ester by a transesterification reaction between fats and alcohols,
A step of producing the fatty acid ester by introducing the fats and oils and the alcohol into a reactor filled with an anion exchanger;
A separation step of separating the produced fatty acid ester from by-products,
A transfer step of transferring the reactor, taking out the anion exchanger from the plurality of reactors, and filling the regenerator for performing a regeneration treatment;
A regeneration step of regenerating the anion exchanger in a regenerator separate from the reactor;
A return step of removing the regenerated anion exchanger from the regenerator, filling the reactor and returning it;
The manufacturing method of the fatty acid ester characterized by having.   The method for producing a fatty acid ester according to claim 1, wherein the reactor is detachable, and the transfer and the return are performed while the anion exchanger is filled in the reactor.   The method for producing a fatty acid ester according to claim 1 or 2, wherein the regeneration step is performed by eluting the fatty acid adsorbed on the anion exchanger and hydroxylating the anion exchanger.   Prior to the production step, a removal step of removing the free fatty acid by using a cation exchanger as a catalyst and producing a fatty acid ester by an esterification reaction between the free fatty acid contained in the oil and fat and the alcohol is further performed The method for producing a fatty acid ester according to any one of claims 1 to 3, comprising: An apparatus for producing a fatty acid ester that uses a anion exchanger as a catalyst and produces a fatty acid ester by an ester exchange reaction between fats and alcohols,
A detachable reactor that mixes the fats and oils, the alcohols and the anion exchanger to produce the fatty acid ester;
A separator for separating the produced fatty acid ester from by-products,
Transfer means for transferring the reactor to a regenerator for performing a regeneration process;
A regenerator separate from the reactor for regenerating the anion exchanger;
A return means for charging and returning the regenerated anion exchanger to the reactor;
An apparatus for producing a fatty acid ester, comprising:   The apparatus for producing a fatty acid ester according to claim 5, further comprising a remover that removes free fatty acids contained in the fats and oils by using a cation exchanger.   The transfer means includes means for sending the anion exchanger to the regenerator after storing the anion exchanger taken out from the plurality of the reactors, and the returning means includes the regenerated anion. 7. The apparatus for producing a fatty acid ester according to claim 5, further comprising means for taking out the exchanger from the regenerator and sending it to the storage.

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