JP6536928B2 - Regeneration treatment of anion exchange resin catalyst for continuous production of fatty acid ester - Google Patents

Description

The present invention relates to a regeneration treatment method of an anion exchange resin catalyst used in a fatty acid ester production method from fat and oil, and a fatty acid ester production method using an anion exchange resin catalyst regenerated by the regeneration treatment method.

BACKGROUND ART Fatty acid esters synthesized by transesterification of fats and oils with alcohols are attracting attention as biodiesel fuels. Compared with conventional petroleum-based diesel fuel (diesel oil), biodiesel fuel has a cleaner exhaust gas when burned, reduced emissions of carbon monoxide, hydrocarbons, particulate matter, etc., and emission gas It has many features such as being free of sulfur oxides and sulfates and having high lubricating performance. In addition, because it can be synthesized from waste edible oil that contributes to environmental pollution, it is also expected as an environmentally friendly waste disposal technology.

The inventor of the present invention, Kitagawa et al., Uses a unique idea that uses an anion resin as a heterogeneous phase solid catalyst, and uses a fatty acid ester synthesis technology to transesterify triglycerides contained in fats and oils at relatively low temperature (50 ° C.) worldwide We are pioneering development (Non-Patent Document 2, Patent Document 1, Patent Document 2).

The ion exchange resin used for producing fatty acid esters as biodiesel fuel is inevitably deteriorated in catalyst performance because adsorption of fatty acid residues to the resin is caused by its use. Therefore, the present inventor has also developed a method of regenerating the catalytic activity of the anion resin used for such continuous synthesis of fatty acid ester by washing with a weak acid solution (Patent Document 3).

JP, 2006-104316, A JP 2007-297611 A JP 2007-14871 A

Biochem. Biophys. Res. Commun., 348, 170 (2006). Bioresource Technol. 98, 416 (2007) Bioresource Technol. 142, 732 (2013)

The conventional methods for regenerating ion exchange resins used in the production of fatty acid esters, as described in the above-mentioned Patent Document 3, Non-patent Document 2 and Non-patent Document 3, have several high-volume solutions stepwise It has a large economic and environmental burden.

As a result of researches for the purpose of solving the above problems, the inventor of the present invention simplifies the steps in the regeneration treatment method of anion exchange resin catalyst for fatty acid ester production from conventional fats and oils, and from the regeneration treatment step. The inventors have found that it is possible to significantly reduce the amount of solution used in the regeneration treatment method and the cost required for the regeneration treatment by reusing the effluent, thus completing the present invention.

That is, the present invention relates to the following aspects.
[Aspect 1]
It is a regeneration treatment method of an anion exchanger used as a catalyst in a method for producing fatty acid esters by transesterification between fats and oils and alcohols having saturated linear or branched hydrocarbon backbone having 1 to 8 carbon atoms. The following steps in sequence:
Process (A): a process in which the same volume of liquid as the supplied liquid is discharged as the alcohol is supplied to the anion exchanger;
Step (B): a solution of the alcohol containing acetic acid, which is supplied as the solution having an acetic acid concentration of 0.86 to 1.3 mol / L is supplied to the anion exchanger A step of discharging an equal volume of liquid;
Step (C): a step in which a solution equal in volume to the supplied liquid is discharged as the mixed solution containing sodium hydroxide and water as the solvent and the alcohol is supplied to the anion exchanger, The process wherein the content of the alcohol in the solvent is more than 0% by volume and 80% by volume or less;
Process (D): a process in which the same volume of liquid as the supplied liquid is discharged as the alcohol is supplied to the anion exchanger;
Step (E): The anion exchanger is again supplied with the discharge liquid containing unreacted fat and oil starting from the discharge in step (A) until the time when 60 to 80% by volume of the total discharge is discharged. Process in which the same volume of liquid as the supplied liquid is discharged,
Said reproduction processing method comprising:
[Aspect 2]
The regeneration treatment method according to aspect 1, wherein in the mixed solution in the step (C), the alcohol is 80% by volume.
[Aspect 3]
An anion exchanger regeneration treatment system for carrying out the regeneration treatment method according to aspect 1 or 2, a reactor filled with a cation exchanger for esterifying free fatty acids contained in a fat material And at least two tower reactors connected in series downstream of the anion exchangers used for transesterification and / or adsorption of triglycerides contained in fats and oils connected downstream thereof, and regeneration treatment, Said system comprising a reactor filled with said anion exchanger.
In the following description (including in the table) and figures in the present specification, the steps (A) to (E) according to the claims of the present application are provided to facilitate the comparison between the method of the present invention and the conventional method. Are denoted as steps (1), (2), (3), (5) and (6) respectively according to the corresponding steps in the conventional method .

In the regeneration treatment method of anion exchange resin catalyst of the present invention, the regeneration treatment process is simplified, and the regeneration treatment method is achieved by reusing the liquid discharged from the regeneration treatment process in the next regeneration treatment as much as possible. It is possible to significantly reduce the amount of solution used for processing and the cost required for the regeneration treatment, and also to reduce the environmental impact.

Furthermore, by reusing the anion exchange resin catalyst regenerated by the method of the present invention as a resin for transesterification / adsorption in continuous production of fatty acid esters from fats and oils, fatty acid esters which are product fuels are substantially continuous. It becomes possible to make a "Merry-go-round system" which continuously manufactures a product fuel from fat and oil and regenerates an anion exchange resin.

Figure 2 shows the process flow of a continuous process for the preparation of fatty acid esters from fats and oils containing free fatty acids (FFA) catalyzed by ion exchange resin. An example of the "merry go round system" for implementing the continuous manufacturing method of fatty acid ester of this invention is shown. It is a system consisting of one column filled with cation exchange resin and three columns filled with anion exchange resin (two columns are fuel production, one column is resin regeneration), and the anion exchange resin filled in the upstream column The operation is switched to mode 1 → 2 → 3 when the activity of the is completely eliminated. An example of the fuel manufacture profile in the continuous manufacturing method of fatty acid ester from fats and oils is shown. The regeneration method is based on the conventional method shown in Table 1, and the change behavior of each component concentration in the product flowing through 2 column reactors (inner diameter 5 cm, length 50 cm) packed with 0.6 kg of anion exchange resin It is. The amount of fatty acid ester obtained in one mode is about 2.7 L from the integral of the shaded portion. An example of the reproduction | regeneration processing profile in the reproduction | regeneration processing method of the conventional anion exchange resin is shown. It is change behavior of each ingredient concentration in the solution which flows out through 1 column type column reactors (inner diameter 5 cm, length 50 cm) packed with 0.6 kg of anion exchange resin. The result of Example 2 (1) is shown. The result of Example 2 (2) is shown. The results of comparing the reprocessing profiles with and without the reuse of the effluent are shown.

Non-patent document 2 and non-patent document 3 described in the prior art (non-patent document 2) used for regeneration treatment of anion exchange resin catalyst used in fatty acid ester production method from fats and oils The outline of) is shown in Table 1. This method comprises the following steps.
(1) Supplying methanol to the anion exchange resin to elute glycerin adsorbed to the resin and recover it as a by-product;
(2) feeding a methanol solution of acetic acid to the anion exchange resin to exchange the fatty acid residue adsorbed to the resin with the acetic acid residue;
(3) An aqueous solution of sodium hydroxide is supplied to the anion exchange resin, and the acetic acid residue adsorbed on the resin is exchanged with a hydroxyl group to activate the resin;
(4) supplying deionized water to the anion exchange resin to remove free hydroxyl groups and sodium acetate;
(5) Methanol is supplied to the anion exchange resin to swell the anion exchange resin.

An outline of one embodiment of the regeneration treatment method of anion exchange resin according to the present invention is shown in Table 2. The main features compared with the above-mentioned conventional method are as follows.

1. The solution containing unreacted fatty acid raw material or product fatty acid ester remaining in the column in the transesterification / adsorption process discharged in the first half of the process (1) is supplied again to the anion exchange resin, The conventional fats and oils as seen in FIG. 3 when the anion exchange resin after regeneration treatment is used for transesterification / adsorption by adding a new step (6) to extrude methanol supplied in 2.) In the continuous production method of fatty acid ester from C., it was possible to produce the product fuel continuously by eliminating the operation time in which only the methanol was discharged first and the fatty acid ester (product fuel) could not be obtained.

Here, the liquid containing unreacted oil and fat in the transesterification / adsorption process including oil and fat raw material etc. is a component of the effluent of step (1) at an appropriate interval by any method and means known to those skilled in the art such as HPLC. It can confirm by analyzing etc. suitably.

In the first half of the process (1), it varies depending on the conditions of the reprocessing process, system conditions, raw material oil and fat components, etc., for example, about 60 to 80 % by volume of the first half of the whole discharged liquid from the process (1) .

2. Increase of reaction efficiency (reduction of production cost) by setting the acetic acid concentration in the methanol solution used in step (2) of the above-mentioned conventional method to 0.8 to 1.4 mol / L, preferably 1.3 mol / L. I

3. Instead of the aqueous solution of sodium hydroxide used in step (3) of the above-mentioned conventional method, a mixed solution with methanol containing water in an amount capable of maintaining the activation reaction efficiency in step (3), Using a mixed solution of water and methanol containing methanol up to about 80% by volume, preferably a mixed solution of water and methanol in a volume ratio of 2: 8 as a solvent of sodium hydroxide, The amount of water used in step (3) of the method was reduced and step (4) of supplying water was eliminated.

Furthermore, in another embodiment of the regeneration treatment method of an anion exchange resin according to the present invention, a method comprising the steps (1) to (3) and (5) shown in the above embodiment, preferably further comprising the step (6) In the method including the above, there is a feature that the effluent from each step of the regeneration treatment is reused in the next regeneration treatment as listed below.

That is, since the effluent discharged in the second half of the step (1) is no longer substantially containing unreacted oil and is a methanol solution containing 60 wt% or more of glycerin, it is a product as high quality glycerin for raw material applications. Turn

In the second half of the process (1), it varies depending on the conditions of the regeneration process, system conditions, raw material oil and fat components, etc., but about 20 to 40 % by volume of the second half of the whole discharge from the process (1) flows out .

Furthermore, since the effluent from step (2) is methanol containing a trace amount of fatty acid released from the resin, it is reused in place of methanol in step (1) of the next regeneration treatment method.

In addition, since the discharge liquid discharged from the step (5) contains methanol, sodium ions and water, the sodium concentration and the water concentration are appropriately adjusted, and then this is adjusted in the step (3) of the next regeneration treatment method. Reuse as a mixed solution of sodium hydroxide, methanol and water.

Furthermore, the effluent from step (6) is reused as part of step (5) of the next regeneration process.

The present invention further relates to a method for continuously producing fatty acid esters from fats and oils, wherein the anion exchange resin regenerated by the above regeneration treatment method is used as a heterogeneous phase solid catalyst. In addition, the continuous production method itself of fatty acid ester from fats and oils is already described in the literature etc. which were mentioned to the prior art literature of this specification. The process flow is shown in FIG.

Specifically, a method of continuously performing transesterification and / or adsorption using a reactor filled with an anion exchange resin is preferable.

As the anion exchanger (anion exchanger), any of those known to those skilled in the art described in JP-A-2006-104316 and JP-A-2007-297611 can be used. In particular, strongly basic anion exchange resins are preferred. When the anion exchange resin is classified according to the degree of crosslinking or the degree of porosity, gel type, porous type, high porous type and the like can be mentioned, but porous type and high porous type are preferable.

In addition, as a commercial item, for example, Diaion PA-306 (made by Mitsubishi Chemical Corporation), Diaion PA-306S (the same), Diaion PA-308 (the same), Diaion HPA-25 (the same) Dowex 1 -X2 (made by Dow Chemical Company), Amberlite IRA-45 (made by Organo company), Amberlite IRA-94 (same), etc. can be used.

Furthermore, as a commercial item of anion exchange resin which satisfies pKa 9.8 or less, for example, Diaion SA20A (made by Mitsubishi Chemical Corporation), Diaion SA21A (the same), and porous type II strong base anion Diaion PA408 (the same), Diaion PA412 (the same) and Diaion PA418 (the same), which are exchange resins, can be used. Here, the type II strong base anion exchange resin refers to the anion exchange resin having the dimethylethanol ammonium group described above.

Since a commercially available anion exchange resin is Cl type at the time of purchase, it is used in the present invention after being substituted with an OH group. For example, 0.5 to 2 mol / L of aqueous NaOH solution is used as the displacing agent, and the flow rate of the displacing agent is preferably about 2 to 10 ml NaOH / min per 1 ml of the anion exchange resin. The amount of liquid used is 5 to 20 ml per 1 ml of anion exchange resin. After the substitution is completed, the resin is removed from the column and thoroughly washed with distilled water so that no substitution agent remains. The pH of the resin washing solution is measured to confirm that it has the same pH as distilled water, and finally, it is washed with a predetermined alcohol and used in the present invention.

The amount of anion exchange resin used is generally 0.1 to 1.0 L, preferably 0.3 to 0.5 L or so, for the amount of oil passing through per 1 kg-wet of resin.

Further, since free fatty acids contained in the oil are adsorbed to the anion resin, when directly treating an oil containing a large amount of the fatty acid, cation exchange is carried out before the oil is brought into contact with the anion exchange resin. It is necessary for the resin to proceed with the esterification reaction of free fatty acids contained in the oil to form an adsorption inactive ester.

As a cation exchange resin, cation resin well-known to those skilled in the art, such as DIAION PK-208LH (made by Mitsubishi Chemical Corporation), can be used, for example.

Various conditions such as reaction time and temperature by the anion exchange resin and the cation exchange resin can be appropriately set by those skilled in the art. For example, the reaction time may be 5 minutes to 2 hours, 0 ° C. to 55 ° C., and about 1 to 10 atmospheres.

The conditions such as reaction time and temperature in the regeneration treatment method and fatty acid ester production method of the present invention and supply conditions such as the flow rate of the treatment liquid are, for example, values described in the present specification and attached drawings. The person skilled in the art can appropriately set accordingly.

There is no restriction | limiting in particular in the fats and oils used as a raw material in the continuous manufacturing method of the fatty-acid ester of this invention method, A natural oil (crude oil), a synthetic oil, or these mixtures may be sufficient. Furthermore, modified oils obtained by modifying a part of these oils by treatment such as oxidation and reduction, and processed oil products containing these oils as main components can also be used as raw materials.

For example, fatty acid oil and deodorized effluent (scum oil) which are by-produced in the refining process of rice bran oil and palm oil, which are conventionally used as raw materials in the conventional method, and which are not used effectively can be used. In addition, it is also possible to use the oil in which arbitrary foreign matter components other than fats and oils are mixed. These foreign components are preferably used in the method of the present invention after being removed by suitable means known to those skilled in the art such as sedimentation, filtration, separation and the like.

Also, instead of methanol used in the method of the present invention, it is also possible to use other alcohols having a saturated linear or branched hydrocarbon backbone having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. It is possible. For example, 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 combination of two or more. Alcohols act as a reaction substrate for alcoholysis (ester exchange reaction) of oils, and also have a solvent action for controlling dilution and viscosity of oils.

In the method for continuously producing a fatty acid ester according to the present invention, transesterification and / or adsorption are continuously carried out using a reactor packed with at least two columns of anion exchange resin connected in series, and the at least two columns are continuously produced. The anion exchange resin is subjected to the regeneration treatment method of the present invention when the catalyst activity of the anion exchange resin packed in the most upstream side reactor of the above disappears, and the most downstream side of the remaining reactors The so-called "Merry-Go-round system (scheme)" is constructed by repeating a cycle consisting of continuing the continuous production method of fatty acid ester by connecting a reactor filled with anion exchange resin regenerated by the above method. can do. An example of this is shown in FIG.

Therefore, the present invention also relates to a system for carrying out a continuous process for the production of fatty acid esters from such fats and oils. The system is, for example, a reactor filled with a cation exchange resin for esterifying free fatty acids contained in fat and oil raw materials, and transesterification reaction of triglyceride contained in fats and oils connected downstream thereof. Alternatively, it includes at least two columns of reactors packed in an anion exchange resin used for adsorption and connected in series, and a reactor packed with anion exchange resin to be regenerated.

In the system of the present invention, more specifically, it is desirable to have a reactor having an inlet for the reaction substrate in one of the containers (reactor) filled with a predetermined ion exchanger, and a recovery port for the product in the other. . The containers may be provided alone, but may have a structure in which a plurality of containers are connected in parallel and / or in series. Further, the shape of the container is not particularly limited, but a column is usually used. In the case where the ion exchange resin is packed in a column and used, in order to prevent the resin from swelling and breakage, a mode using an expanded bed packed bed having a high porosity is preferable. Here, the expanded bed column is used in a separation and purification method in which a target component dissolved in a fluid containing high viscosity fluid or solid content is adsorbed to adsorbent particles and recovered, and the inside of the column is Flowing fluid upwards, floating adsorbent particles with large specific gravity, and performing column chromatography operation with large porosity maintained, for example, Chemical Engineering Journal Vol. 27 No. 2 (2001) pp. 145-148 etc. can be used known methods. In the range of large molar ratio of oils to alcohols, the problem of breakage of ion exchange resin due to swelling is likely to occur, so the reactor design is noted. However, for efficient operation, in the case of the reaction / adsorption operation in which the mixture of oil and alcohol is passed, the upflow is used, and in the case of resin regeneration in which the mixture of acid and alcohol is passed, the downflow It is preferable to use

Hereinafter, the present invention will be specifically described based on examples, but the technical scope of the present invention is not limited by these descriptions. The following examples were carried out according to the general methods known to those skilled in the art unless otherwise specified.

[Effect of step (6) in the method of regenerating treatment of ion exchange resin of the present invention]
In the step (6) in the regeneration treatment method of the ion exchange resin of the present invention, a liquid containing unreacted oil / fat raw material or product fatty acid ester remaining in the column in the transesterification / adsorption process discharged in the step (1) Were supplied to the anion exchange resin, and the effect of extruding the methanol supplied in step (5) was verified under the following conditions. One column (diameter 5 cm × length 100 cm) packed with cation exchange resin Diaion PK208LH and two columns (diameter 5 cm × length 50 cm) packed with 0.6 kg-wet of anion exchange resin Diaion PA 306 S The reaction system connected in series was maintained at 50 ° C., and a raw material solution in which crude Jatropha oil (free fatty acid content: 30 wt%) and methanol were mixed at a stoichiometric ratio was supplied at 100 cm ³ / h.

Figure 1 shows the fuel production profile (the time course of the amounts of fatty acid methyl ester (FAME produced, triglycerides (TG) and free fatty acids (FFA) produced) in the continuous production process of fatty acid esters from fats and oils as shown in FIG. It showed to 3.

Here, when the above-mentioned step (6) is not carried out, the profile shown in FIG. 3 (the part of the horizontal axis 0-3.8, unreacted TG) is actually obtained even if continuous production and regeneration are carried out using the merry-go-round system. The part where is not detected) is repeated. That is, the operation is a semi-batch operation, and only the methanol flows out in the portion of the horizontal axis 0-0.8, and no product is obtained. That is, no product can be obtained at 21% of the manufacturing operation time.

On the other hand, by adding the step (6), the area on the left side of the broken line in FIG. 3 shifts to the regeneration step, and the manufacturing step becomes a repetition of the portion on the horizontal axis 0.8-3.8, substantially continuous. It is possible to produce product fuel.

When the merry-go-round system as shown in FIG. 2 is used, the regenerated column is connected to the most downstream side of the merry-go-round manufacturing column. The reaction liquid remaining in the column after the above step (6) is a liquid containing unreacted fatty acid raw material and product fatty acid ester in the transesterification / adsorption process discharged in step (1) by the regeneration treatment method of the present invention And at least half or more of the reaction has proceeded by the regenerated ion exchange resin. Therefore, when this is returned to the post-regeneration column connected to the most downstream of production, the reaction rate is 100% even if only one column passes, and production of product fuel from fats and oils and anion exchange resin It becomes possible to construct a merry-go-round system that continuously performs reproduction.

[Acetate Concentration in Methanol Solution Used in Step (2) in Regeneration Treatment Method of Ion Exchange Resin of the Present Invention and Effect of Mixed Solution of Water and Methanol Used in Step (3)]
The following examination was performed based on the reproduction | regeneration processing profile (FIG. 4) in the reproduction | regeneration processing method (nonpatent literature 2) of the conventional anion exchange resin.

First, the fluctuation of the amount of free fatty acid discharged by changing the acetic acid concentration in the methanol solution used in the step (2) was measured, and the efficiency of the reaction (reduction of the production cost) was examined. The results are shown in FIG.

According to it, the range of acetic acid concentration in the methanol solution used in step (2) is higher than the conventional 0.43 mol / L, for example, about 0.8 to 1.4 mol / L, preferably about When the concentration is 1.3 mol / L, the total amount of acetic acid used is increased, but the required methanol solution is needed, because the concentration of free fatty acids (denoted as “FH” or “FFA”) to be eluted increases rapidly. As a result, the cost of the entire reagent used in step (2) was reduced, and the reaction could be made more efficient.

Next, the influence of using a mixed solution of water and methanol instead of the aqueous solution used in step (3) of the above-mentioned conventional method was examined. The results are shown in FIG.

According to this, in a mixed solution of water and methanol containing methanol up to about 80%, particularly in a mixed solution of water and methanol in a volume ratio of 2: 8, the concentration of free hydroxyl groups is the same as in an aqueous solution of sodium hydroxide It turned out to be maintained. Therefore, in step (3), by using a mixed solution of sodium hydroxide and water and methanol instead of the conventional aqueous solution of sodium hydroxide, the step while substantially maintaining the activation reaction efficiency by the hydroxyl group It is possible to reduce the amount of water used in (3), eliminate the need for step (4), and further reduce the time required for step (5).

FIG. 7 shows a regeneration treatment profile obtained by adding the above improvement to the regeneration treatment method of the conventional anion exchange resin (the step (4) in the prior art is eliminated). As apparent from the comparison between this and the regeneration treatment profile in the conventional anion exchange resin regeneration treatment method shown in FIG. 4, the regeneration treatment cost is maintained while maintaining the same degree of regeneration treatment efficiency as the prior art. From the 159.5 yen / L-FAME (fatty acid ester) of the above, a remarkable effect of reducing to 125.7 yen / L-FAME by the above modification was obtained (Table 3). In any of the processing methods, the amount of fatty acid ester produced in each mode of fuel production is about 2.7 L, and the cost per 1 L of fatty acid ester can be determined from this value.

[Effects of Reusing Effluent from Each Step of Regeneration Treatment in the Next Regeneration Treatment]
In the improvement technology of the conventional anion exchange resin regeneration treatment method according to the present invention described in Example 2, the influence of reusing the discharge liquid from each step of the regeneration treatment in the next regeneration treatment is further examined. did.

First, based on the composition of the discharge liquid from each regeneration processing step of the improvement technology (FIG. 7) of the anion exchange resin regeneration processing method according to the present invention, the reuse rate in the case of reuse in the next regeneration processing was examined. The results are shown in Table 4.

Furthermore, the regeneration treatment profile and the regeneration treatment cost were compared in the case where the reuse of the effluent shown in Table 4 was performed and in the case where it was not performed (Table 5). The amount of fatty acid ester produced in each mode of fuel production remains unchanged at about 2.7 L, and the cost per 1 L of fatty acid ester can be determined from this value. As a result, it was confirmed that the same regeneration treatment profile was obtained in both cases, and the regeneration treatment capacity of the anion exchange resin was not substantially reduced even when the effluent was reused. On the other hand, by carrying out the reuse of the effluent, the total amount of solution used in the regeneration treatment method was significantly reduced, and it was possible to reduce the production cost of fatty acid ester by 68.5%. In addition, the environmental load was able to be reduced by reusing the effluent.

According to the present invention, it is possible to significantly reduce the cost of fatty acid ester production for biodiesel fuel, and to produce it at lower cost and with less environmental load than the cost of producing a commercial diesel fuel.

Claims (3)

It is a regeneration treatment method of an anion exchanger used as a catalyst in a method for producing fatty acid esters by transesterification between fats and oils and alcohols having saturated linear or branched hydrocarbon backbone having 1 to 8 carbon atoms. The following steps in sequence:
Step (A): Due to supplying the alcohol to the anion exchanger, the step of liquid equal volume and the supplied liquid is discharged;
Step (B): A solution of the alcohol containing acetic acid, with the solution concentration of acetic acid is 0.86~1.3mol / L to be supplied to the anion exchanger, and the supplied liquid A step of discharging an equal volume of liquid ;
Step (C): with a mixed solution containing the water alcohol as sodium hydroxide and a solvent to be supplied to the anion exchanger, comprising the steps of liquid equal volume and the supplied liquid is discharged, the content of the alcohol is 80% by volume or less 0 volume% excess solvent, the process;
Step (D): With the supplying the alcohol to the anion exchanger, the process liquid of equal volume and the supplied liquid is discharged; and step (E): from the start of discharge in the step (A) up to the point of 60 to 80 volume% of the total effluent is discharged, the effluent containing unreacted oil feedstock, with the supplied again to the anion exchanger, the liquid of equal volume and the supplied liquid is discharged The process to be
Said reproduction processing method comprising: The regeneration treatment method according to claim 1, wherein in the mixed solution in the step (C), the alcohol is 80% by volume. It is the reproduction | regeneration processing system of the anion exchanger for enforcing the reproduction | regeneration processing method of Claim 1 or 2, Comprising: The reaction with which the cation exchanger for esterifying the free fatty acid contained in fats and oils raw material was filled. And at least two tower reactors connected downstream of the anion exchanger, which are connected downstream of the anion exchangers used for transesterification and / or adsorption of triglycerides contained in fats and oils, and regeneration treatment, Said system comprising a reactor packed with said anion exchanger.