JP3071639B2 - Method for producing liquid oil by transesterification - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for continuously producing a liquid oil using a transesterification reaction of an oil or fat using an immobilized lipase.

[0002]

2. Description of the Related Art The transesterification of fats and oils for the purpose of changing the properties of raw material fats and oils by substituting fatty acid residues constituting fats and oils with other fatty acid residues and obtaining fats and oils having desired properties is carried out by: Conventionally, an alkaline catalyst has been used. However, in this method, the fatty acid residues at the 1, 2, and 3 positions of triglyceride are completely replaced at random, so that the type of triglyceride is increased and the yield of a desired liquid oil is reduced. Did not. On the other hand, it is reported that when a reaction tower is filled with immobilized lipase having reaction specificity only at the 1st and 3rd positions and transesterification is carried out through raw oils and fats, the liquid oil yield increases as the reaction rate increases. 61-29338
No. 9). This is because solid fatty acids have a large amount of unsaturated fatty acids at the second position.

[0003] The transesterification of fats and oils using such lipases is carried out in a batch system in which the fats and oils and the immobilized lipase are brought into contact in a reaction vessel or in a reaction tower filled with the immobilized lipases. It is performed by the method of introducing. Of these, according to the method using a reaction tower, the desired fats and oils can be obtained continuously, but the transesterification activity of the immobilized lipase decreases with the progress of the transesterification reaction. The immobilized lipase that had been packed in the had to be replaced. still,
As a method using a reaction tower, a multi-stage method using a plurality of reaction towers has also been proposed (enzyme engineering (1981)), but this was merely for stabilizing the system. On the other hand, since the conventional immobilized lipase has a short life, a method of transesterifying fats and oils using the immobilized lipase has not been industrialized yet. Therefore, early industrialization of a continuous transesterification method of fats and oils using immobilized lipase is desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a continuous liquid oil by transesterification of fats and oils using an immobilized lipase which can be used industrially.

[0005]

According to the present invention, a fat / oil raw material having a specific water content is introduced into a multi-stage reaction column having a plurality of reaction columns arranged in series so as to pass through the reaction column at a specific speed, And when the performance of the immobilized lipase is degraded and the transesterification capacity is reduced, the oil and fat raw material to be supplied to the front row reaction tower is supplied to the next reaction tower and a new reaction tower is provided at the bottom of the multi-stage reaction tower. It has been made based on the finding that the above problem can be efficiently solved if the ester exchange reaction is continued by connecting in series. That is, the present invention relates to a method in which an oil / fat raw material is passed through a multi-stage reaction tower which is arranged in series with at least two reaction towers each having an immobilized lipase having a reaction specificity at positions 1 and 3 of triglyceride, and When a transesterification reaction is carried out to produce a liquid oil,
LHSV for all reaction towers is 0 ppm or more
When the transesterification capacity of the immobilized lipase is reduced under the conditions of 0.7 to 10 and when the transesterification ability of the immobilized lipase is reduced, the fat and oil raw material supplied to the front row reaction tower is supplied to the subsequent reaction towers and the multi-stage reaction tower A method for producing a liquid oil, characterized in that another reaction column filled with a new immobilized lipase is connected in series at the last stage of the step (a) to continue the transesterification reaction.

The lipase having reaction specificity at the 1- and 3-positions of triglyceride used in the present invention includes lipases derived from microorganisms such as Mucor, Rhizopus, Aspergillus, Alcaligenes and Penicillium. Among them, it is particularly preferable to use a lipase of the genus Mucor or Rhizopus. In the present invention, an immobilized lipase in which the above lipase is immobilized (supported) on a carrier is used. Here, any carrier can be used, but it is preferable to use a resin having a functional group that forms a covalent bond with lipase in an aqueous solution and a weakly basic anion exchange group as the carrier. Examples of such a resin include divinylbenzene (DVB) -based copolymer, methacrylate, acrylate, polypropylene,
Examples of the base material include nylon and phenol, and a divinylbenzene copolymer is particularly preferable. The resin has a pore size of 5 nm to 1000 nm, preferably 10 nm to 1000 nm.
nm to 1000 nm is suitable. The carrier may have any particle size, but it is generally preferable to use a carrier in which 90% or more of the carrier has a particle size of 50 to 1,000 μm. In particular, it is preferable to use those having an average particle size of 300 to 600 μm.

[0007] Examples of the functional group of the resin that forms a covalent bond with an enzyme in an aqueous solution include an epoxy group, a cyanide group, an aldehyde group, and a triazinyl group.
Of these, an epoxy group is preferable, and a 1,2 epoxy group in which an oxygen atom is added to adjacent carbon is particularly preferable.
Examples of the anion exchange group possessed by the resin include a primary amino group, a secondary amino group, a tertiary amino group and a quaternary ammonium group, and a weakly basic tertiary amino group such as diethylamino group. An ethyl group (DEAE group) and a dimethylamino group are preferred. The content or the ratio of the functional group and the anion exchange group in the resin carrier can be arbitrarily set, but the functional group forming a covalent bond to be copolymerized contains 0.05 to 5.0 mol / kg. It is preferably 0.1 to 2.0 mol / kg. Further, it is preferable to contain 0.05 to 5.0 mol / kg of an anion exchange group, particularly preferably 0.1 to 2.0 mol / kg. These functional groups and anion exchange groups can be introduced into the resin by a conventional method. For example, monomers having these functional groups or anion exchange groups were introduced by co-existing and copolymerizing during the polymerization of the resin, and the above-mentioned resin or a pre-treatment of the resin to form a reactive functional group. For example, it can be introduced by a general chemical bonding method such as an ester bond.

[0008] As a resin into which the above-mentioned specific functional group and anion exchange group are introduced by such a method, for example, Levatit R260K available from Bayer can be obtained. In addition, Levatit R260K has an epoxy group and a secondary amino group, but a resin having an epoxy group and a tertiary amino group is a more preferable carrier resin. The transesterification activity of a preferred immobilized lipase is 150 units or more per 1 g (dry weight) of the immobilized lipase. There are various methods for measuring the transesterification activity. Here, palm olein 50 is used.
mM, myristic acid 50 mM, water 100-150 ppm
Is used as a substrate, and 20 to 200 mg (dry basis) of immobilized oxygen is added to the substrate and reacted at 50 ° C. The activity to reduce 1 μmol of acid is defined as 1 unit.

[0009] Such an immobilized lipase can be prepared by any method, but it is preferable to bring the lipase into contact with the resin carrier in the presence of a fatty acid or a derivative thereof. Examples of such a fatty acid or a derivative thereof include a fatty acid or a derivative thereof such as a fatty acid ester and a fat and oil, and a reaction raw material or a part thereof or a product thereof, or a substrate or a similar substance to a reaction raw material that can be a product of an enzyme. Fatty acids or fats and oils can be used, and preferably, a raw material for a transesterification reaction is used. Examples of these include rapeseed oil, soybean oil, corn oil, palm oil, their fractionated oils, oleic acid, lecithin, fatty acid mono- or diglycerides, and the amount used is 1 to 100% by weight based on the carrier. Preferably 5
30% by weight.

In the present invention, when producing a liquid oil by performing a transesterification reaction, a raw material having a water content of 700 ppm or more is used. Preferably, 700-2000 ppm,
More preferably, the transesterification reaction is carried out in a 1000 to 1700 ppm fine water system. In addition, a suitable transesterification reaction is performed at a temperature of 30 to 70 ° C., and an organic solvent can be used if necessary. The organic solvent to be used is selected from those which do not decrease the activity of the immobilized enzyme, and examples thereof include n-hexane and petroleum ether. In addition, when using a liquid fat as a raw material fat, transesterification can be performed, without using an organic solvent. Further, even when a solid fat or oil is used, the transesterification reaction can be performed by heating and melting to make a liquid state. The target fats and oils include ordinary fats and oils such as coconut oil, soybean oil, rapeseed oil, palm oil and olive oil, lecithin, fatty acids and their derivatives, and especially plant-derived fats and oils, lecithin and fatty acids. Although suitable, animal fats and oils, fish and shellfish fats and fats thereof can also be used. The combination of raw materials for the transesterification reaction is a fat or oil and a fatty acid or an ester thereof, or one or more fats and oils. Of these, as fats and oils raw materials,
A mixture with at least one fat selected from the group consisting of coconut oil and palm oil and at least one fat selected from the group consisting of soybean oil and rapeseed oil is preferred.

In the present invention, the above-mentioned immobilized lipase and the raw material for fats and oils are used, and at least two reaction towers, preferably three to three, are used.
The oil / fat raw material is passed through a multi-stage reactor in which eight reactors are arranged in series at a speed LHSV of 0.7 to 10 which passes through the reactor. Preferably, LHSV is 0.
8 to 8. Here, the LHSV means a space velocity (velocity per hour) based on the liquid, and can be easily obtained by dividing the liquid passing capacity per hour by the volume of the space filled with the catalyst. In the present invention, further, when the transesterification ability of the immobilized lipase is reduced, the fat and oil raw material to be supplied to the front column reaction column is supplied to the next reaction column, and a new immobilized lipase is provided at the bottom of the multi-stage reaction column. Is connected in series to continue the transesterification reaction. Here, when the transesterification ability of the immobilized lipase is reduced, the transesterification rate at the outlet of the last reactor is reduced to about 60%, preferably to 70%, but is not limited thereto. However, the reaction efficiency can be arbitrarily determined in consideration of economy. Here, the transesterification rate is a value obtained by measuring the content of a triglyceride having 53 carbon atoms before the reaction and at the time of substantial reaction equilibrium, and calculating 0% before the reaction and 100% at the time of substantial reaction equilibrium. is there

Incidentally, as the reaction tower, a vertical type, a horizontal type or the like can be used arbitrarily. Also, the flow direction may be an upflow, a downflow, or a radial flow. In addition, a fixed bed or an expanded bed can be used as appropriate as the filling type. In the present invention, various liquid oils having a melting point of −20 ° C. to 20 ° C., such as salad oils and freeze-resistant oils and fats, can be produced by the above method. Of these, salad oil is preferably produced. In addition, salad oil is 0 based on Japanese Agricultural Standards.
It is a liquid oil having cooling resistance that satisfies the condition that no clouding occurs for 5.5 hours even at ° C. Salad oil yield can be measured by the following method. The transesterified liquid oil is slowly cooled to 3 to 10 ° C., preferably to about 5 ° C. over about 48 hours without solvent, and the solid component (solid fat) which is deposited in the cooled product is cooled. After filtration and separation by a conventional method at the same temperature, the yield of the obtained liquid part (= salad oil) is measured. The salad oil yield will be determined from this.

[0013]

According to the production method of the present invention, it is possible to make the treated oil a desirable property in a large amount. Next, the present invention will be described with reference to examples.

[0014]

【Example】

Example 1 Divinylbenzene-based hydrophobic resin FE1025 having an epoxy group and a DEAE group as carrier (glycidyl methacrylate, diethylaminoethyl methacrylate and divinylbenzene copolymerized at a raw material weight ratio of 25:25:50 (Organo Corporation) 2) was suspended in 1 liter of ion-exchanged water, and 0.4 kg of rapeseed oil was added thereto to treat the carrier. Next, lipase F was previously added to this solution.
-AP15 (derived from Rhizopus oryzae; Amano Pharmaceutical Co., Ltd.)
Aqueous solution obtained by dissolving 0.4 kg of the product (made by the company) in 20 liters of ion-exchanged water was added, and mixing was continued for 4 hours. Thereafter, the mixture was filtered and dried under reduced pressure to obtain about 2 liters of immobilized lipase. Three reaction towers having a catalyst filling inner volume of 30 ml were prepared,
Each reaction column was filled with 30 ml each of the immobilized lipase moistened with rapeseed oil. After the three reaction towers are connected in series (referred to as a first-stage reaction tower, a second-stage reaction tower, and a third-stage reaction tower from the top), rapeseed oil and palm oil in a ratio of 6: 4 (weight). ), A feedstock having a water content of 1500 ppm and a temperature of 50 ° C was introduced into the reaction tower at an LHSV of 1.0 with respect to all the reaction towers, and a transesterification reaction was carried out by a continuous flow system. At this time, warming was performed with warm water so that the temperature of each reaction tower was maintained at 50 ° C.

The conversion was 96% at the initial stage, but dropped to 70% when oil passing was continued for 160 days.
At this time, the immobilized lipase in the first-stage reaction column is taken out, filled with the new immobilized lipase, and connected to the third-stage reaction column behind (referred to as the fourth-stage reaction column). Then, the feedstock was introduced into the second-stage reaction tower, and the reaction was continued. As a result, the conversion was 90%. After that, oil passing was continued for another 96 days, resulting in a reaction rate of 70%. At this point, the immobilized lipase in the first reaction column (second stage reaction column) is again taken out, filled with the new immobilized lipase, and ligated to the rear of the fourth stage reaction column (first stage). As a result, the reaction rate was again 90%. In this state, when the transesterification reaction was continued again for 96 days, the reaction rate dropped to 70% again. 96 after
The above operation was repeated twice a day, but the reaction rate was not different from the above transition. The total amount of newly used immobilized lipase from the first switching to immediately before the fourth switching in the above operation was 90 ml, and during that period (288
Days) the treated oil was 622 liters. That is, this means that 6900 times of the treated oil is obtained per immobilized lipase volume. This treated oil had a conversion of 82% and a salad oil yield of 81%.

Example 2 The reaction was carried out under the same conditions as in Example 1 except that the internal volume of the catalyst charged in one column was 6 ml and the LHSV was 4.0. However, the time for switching the reaction tower was set to the same date and time as the amount of oil flow. That is, the first time was performed on the 40th day and the second and subsequent times were performed from the switching to the 24th day and performed until the fourth switching. The treated oil obtained from the first switch to immediately before the fourth switch (72 days) is 1
At 24 liters, the conversion was 63%, and the salad oil yield was 83%.

Example 3 Following Example 1, (from the point of the fifth switching in Example 1), only LHSV was changed to 0.7 and the reaction was carried out.
Continued for 137 days. The treated oil obtained during this time was 207
Liters (immobilized lipase newly used during this period is 3
0 ml, so 6 per immobilized lipase volume
The reaction rate was 86%, and the salad oil yield was 75%.

Example 4 A reaction was carried out under the same conditions as in Example 2 except that the LHSV was changed to 8. However, the time for switching the reaction tower was set to the same date and time as the amount of oil passed per unit volume of the immobilized lipase. That is, the first time was performed on the 20th day, the second and subsequent times were performed on the twelfth day from the switching, and were performed until the fourth switching. The treated oil obtained from the first switch to immediately before the fourth switch (36 days) was 124 liters, the reaction rate was 43%, and the salad oil yield was 77%.

Example 5 The reaction was carried out under the same conditions as in Example 2 except that the water content was changed to 800 ppm. 124 liters of treated oil obtained from the first switching to immediately before the fourth switching (72 days), the reaction rate was 54%, and the salad oil yield was 77%.

Example 6 Immobilized lipase was prepared in the same manner as in Example 1 using 200 liters of a carrier and 40 g of rapeseed oil using 2 liters of aqueous lipase paratase M1000L (derived from Mucor Mihai, manufactured by Novo Nordisk Bioindustry). A reaction was carried out using the above-mentioned immobilized lipase under the same conditions as in Example 2. 124 liters of the treated oil obtained from the first switching to immediately before the fourth switching (72 days) had a reaction rate of 51% and a salad oil yield of 76%.

COMPARATIVE EXAMPLE 1 Using a simple reactor having a catalyst-filled inner volume of 6 ml, a raw material oil, immobilized lipase, and reaction conditions (LHSV:
4.0) was operated for 72 days (6900-fold treatment per immobilized lipase volume) in the same manner as in Example 2. The obtained treated oil was 41 liters, the conversion was 54%, and the salad oil yield was 72%, which was clearly lower than that of Example 2 in the switching operation.

Comparative Example 2 The reaction was carried out under the same conditions as in Example 2 except that LHSV was changed to 12. However, the time for switching the reaction tower was set to the same date and time as the amount of oil flow. That is, the first time was performed on the thirteenth day, and the second and subsequent times were performed on the eighth day from the switching, and were performed until the fourth switching. The treated oil obtained from the first switching to immediately before the fourth switching (24 days) had a very low conversion of 30% and a salad oil yield of only 68%.

Comparative Example 3 The reaction was started under the same conditions as in Example 2 except that the water content was changed to 500 ppm. The reaction rate, which was 84% at the beginning of oil passing, dropped to almost 0% by the 40th day, so oil feeding was discontinued thereafter.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshimi Shirato 3-13 Moriyacho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Chiyoda Research Institute, Ltd. Chiyoda Research Park (72) Inventor Noboru Ando Moriyacho, Kanagawa-ku, Kanagawa Prefecture 3-chome 13 Chiyoda Chemical Works Construction Co., Ltd. Chiyoda Research Park (72) Inventor Haruhito Kobayashi 3-13 Moriyacho, Kanagawa-ku, Yokohama-shi, Kanagawa Chiyoda Chemical Works Co., Ltd. Chiyoda Research Park (58) Investigated field (Int .Cl. ⁷ , DB name) C12P 7/64

Claims (5)

(57) [Claims] 1. An oil / fat raw material is passed through a multi-stage reaction column in which at least two reaction columns filled with immobilized lipase having reaction specificity at positions 1 and 3 of triglyceride are arranged in series. In producing a liquid oil by performing a transesterification reaction, an oil / fat raw material having a water content of 700 ppm or more was introduced under the condition that the LHSV of all the reaction towers was 0.7 to 10, and the transesterification ability of the immobilized lipase was reduced. When the fat and oil raw material that had been supplied to the reaction column in the front row was supplied to the subsequent reaction columns and another reaction column filled with a new immobilized lipase was connected in series to the last stage of the multi-stage reaction column, and connected in series. A method for producing a liquid oil, wherein the transesterification reaction is continued. 2. The immobilized lipase comprises a polymer having a functional group having a covalent bond and a weakly basic anion exchange group, on which a lipase having reaction specificity at the 1- and 3-positions is immobilized. 2. The production method according to 1. 3. The method according to claim 1, wherein the lipase is a lipase derived from a microorganism belonging to the genus Rhizopus or Mucor. 4. The oil / fat raw material is a mixture with at least one oil / fat selected from the group consisting of coconut oil and palm oil, and at least one oil / fat selected from the group consisting of soybean oil and rapeseed oil. The method according to any one of claims 1 to 3. 5. The method according to claim 1, wherein the obtained liquid oil is salad oil.