JP2009183198A - Fermented oil and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oil and fat enabling the combustion in an internal combustion engine and hardly promoting carcinogenesis when being eaten by decreasing the pour point of the oil and fat and lowering the oxidation degree. <P>SOLUTION: The production method for providing a reduced-type oil and fat having the low pour point includes enzymically cleaving an ether bond of glyceride and a fatty acid constituting the oil and fat, cleaving the chain structure by the irradiation with a micro wave, and stabilizing the product with bioethanol. An excellent and inexpensive fuel mild to the environment is achieved, and a healthy oil containing vitamin A, coenzyme Q10 or the like is provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to low pour point and low oxidation of fats and oils.

  Oils and fats include vegetable oils and animal oils such as rapeseed oil, sunflower oil, soybean oil and palm oil. Biomass-derived fuel is obtained by absorbing and fixing carbon dioxide in the atmosphere by photosynthesis, and carbon dioxide emitted by combustion originally exists in the atmosphere. It is evaluated as carbon neutral in that the cycle of fixation and emission is quick and generally does not increase the amount of carbon (carbon dioxide) in the atmosphere. The concept of carbon neutral is used to evaluate the environmental improvement effect of biodiesel. It is very important.

  Due to the different origins of fats and oils, characteristics such as oxidation resistance and low-temperature flow characteristics of fats and oils change, and many of the characteristics depend on the fatty acid composition of the fats and oils. The fatty acid of fats and oils converted into a methyl ester has characteristics such as oxidation resistance and low-temperature fluidity that are almost the same as those of fatty acids. The basic chemical structure of fats and oils is a triglyceride with a large molecular weight in which glycerol and three fatty acids are ether-bonded. The problems of high viscosity and high flash point as a fuel for oils and fats are due to the large molecular weight, and in order to improve this, it is necessary to lower the molecular weight of triglycerides. In many countries, biodiesel is defined as a monoalkyl ester, and thus a low molecular weight process must be employed to produce biodiesel so that the monoalkyl ester is finally produced.

  Fats and oils do not contain aromatic compounds unlike fossil fuels such as light oil, so there are no reports of short-term or chronic toxicity, but the long-chain structure of fatty acid molecules that make up glycerin when eaten is huge It has been reported that human cells have an action of promoting canceration of cells as an oncogenic promoter after undergoing an initiation action with a certain carcinogen. The pour point can be lowered by making the fatty acid molecular structure of glycerin as small as possible. In addition, the oncogenic promoter activity can be lowered by lowering the degree of oxidation of fatty acids.

  The low temperature flow characteristics of fats and oils are described. Internal combustion oils and fats are classified into 5 classes from No. 1 to No. 3 according to kinematic viscosity, pour point, CFPP (Cold Filter Plugging Point), and flash point. The low temperature flow characteristics as a fuel property of light oil are defined by cloud point, pour point, and CFPP. When the light oil is cooled, a wax having a high melting point, which is an ester of a long-chain fatty acid and a long-chain monohydric alcohol, starts to precipitate, and this temperature is called a cloud point (CP). When further cooled, the precipitated wax grows and reaches a pour point (PP) at which the entire light oil loses its fluidity. The wax crystal grows after nucleation, grows discontinuously by repeatedly forming and stopping the crystal plane, and usually shows a coarse rhomboid plate-like crystal of 200 μm. This further adheres to each other to form a three-dimensional network structure. By adsorbing and absorbing a large amount of oil there, the fluidity of the whole oil is lost, and it is said that the fats and oils coagulate with about 2% wax precipitation. The cloud point (CP) and pour point (PP) of fuel refined with vegetable oil having a high saturated fatty acid content such as palm oil show high values. In particular, the influence of stearic acid methyl ester is remarkable. Such low-temperature flow characteristics of fuel hinder the spread of fuel, and the development of this improvement method is urgently needed.

  Oxidative stability (OSI) will be described. Unsaturated fatty acid methyl esters in fuel, especially methyl esters of linoleic acid and linolenic acid, are susceptible to oxidation, and oxidation stability is highly dependent on their content. Since oxidation causes deterioration of the fuel device, it is necessary to manufacture a product having a low degree of unsaturation and extremely high oxidation stability. In order to improve low-temperature flow characteristics, it is expected that long-chain fatty acids are separated from glycerides as much as possible, and at the same time, a high content of saturated fatty acids that improve oxidative stability (OSI: Oxidative Stability Index).

  The biodiesel production methods to date include the following methods. The first is an alkali catalyst method. As a method for reducing the molecular weight of triglyceride, an alcholysis reaction in which monohydric alcohol such as methanol, ethanol, isopropanol or the like is substituted for glycerol of polyhydric alcohol is adopted as a standard method. In the reaction using methanol and the alkali catalyst NaOH, this reaction proceeds reversibly and sequentially. The fats and methanol in the reaction system do not mix and form a heterogeneous phase. The operating factors affecting this heterogeneous reaction include temperature, catalyst concentration, molar ratio of fat and methanol, and stirring strength. The catalytic reaction of monoglyceride is reversible, and rapid glycerol separation is essential to promote the reaction in the forward direction. Next, washing with water for the purpose of removing the alkali catalyst is generally performed. However, the method aiming at lowering the pour point of fats and oils in the alkali catalyst method requires a plurality of reactions and involves an oxidation reaction in the reaction process, so it is a problem that an additional reduction reaction needs to be added. It is.

  The second is a method using an acid catalyst and a solid catalyst. When an acid catalyst is used, esterification of free fatty acid and alcholysis of triglyceride occur simultaneously, and pretreatment of free fatty acid becomes unnecessary as in the case of using an alkali catalyst. However, no industrial production of fuel using an acid catalyst has been performed so far. This is because the reaction using an acid catalyst is significantly slower than the reaction using an alkali catalyst.

  The third is the two-stage supercritical methanol method (Saka-Dadan method). Supercritical methanol has the function of causing esterification of free fatty acids and alcholysis of triglycerides without using a catalyst. In addition, it is a method that can convert various raw materials such as waste cooking oil into fuel without being affected by 30% of water in the raw materials. In the supercritical state (350 ° C., 20-40 MPa), hydrophobic oil and methanol solvate to form a uniform reaction system. This significantly improves the reaction rate. However, it has been found that the double bond of the unsaturated fatty acid produced under this reaction condition changes from cis form to trans form. This bonding state increases the melting point of the fatty acid methyl ester and adversely affects the low temperature fluidity.

  The fourth is fuelization by homogeneous reaction using THF (tetrahydrofuran). Tetrahydrofuran (THF) is non-toxic and inert, soluble in water, alcohols, esters and hydrocarbons, has a density of 0.8892 g / mL, has a boiling point of 67 ° C and is very similar to the physical properties of methanol. Yes. In this reaction system, the separation of the methyl ester phase and the glycerol phase occurs more quickly than in the THF-free system, and since the boiling points of THF and methanol are almost the same, these separations from the ester phase and the glycerol phase are It can be done in the same way as a heterogeneous system. However, in this reaction system, the cost of the furan compound is high and there are many problems.

  Light oil is a fuel that is fractionated from petroleum in the refining process. It is difficult to dilute because it has a weak affinity with ethanol and is difficult to mix with each other.

Since palm oil is refined by boiling after squeezing, fatty acid is oxidized and toxic, and has a carcinogenic promoter activity. Palm oil is an orange-colored oil that is solid at room temperature and has a unique aroma and sweetness. The main components are palmitic acid, oleic acid, linoleic acid, and other stearic acid and myristic acid. Unusual in vegetable oils, it is solid at room temperature and contains a lot of palmitic acid, which is a saturated fatty acid, so the overall composition is close to beef tallow. The orange color of palm oil is derived from beta-carotene, and the original palm oil is rich in beta-carotene. Since retinoic acid, vitamin A, coenzyme Q10, etc. are boiled in the purification stage, they lose their color and become white. Palm oil has the advantage of such a health maintenance supplement and the disadvantage of being easily oxidized due to its long fatty acid linear structure.
Japanese Patent Application No. 2007-117746 Japanese Patent Application No. 2007-149802 Midusuji patent US 6.420.165 B1 Sadayori Hoshina, Masami Morotomi, and I. Bernard Weinstein. 1991. Effect of a Fecapentaene on protein kinase C. Biochemical and Biophisical Research Communications. 176: 505-510.

  The subject of the present invention is that the enzyme cleaves the ether bond between fatty acid and glycerin in fats and oils while preventing oxidation of fatty acid, and further promotes the reaction by irradiating with microwave, mixing bioethanol to lower the pour point and unsaturated. It is to convert the fats and oils to low oxidation molecules at a reduced degree.

  The present inventor has eagerly studied to solve the above problems, and when an enzyme is allowed to act on oils and fats, microwaves are irradiated, bioethanol is mixed, and the pour point is measured. This completes the present invention.

According to the present invention, the lowering of the pour point of oil and fat and the degree of unsaturation can be lowered by mixing the enzyme with microwave irradiation and bioethanol, so that the apparatus becomes inexpensive and there is no problem of residual chemical substances because no so-called chemical catalyst is used. Since the CO ₂ emission amount is carbon neutral, it is possible to provide oils and fats with low environmental impact. Moreover, since the oxidation of the fatty acid in fats and oils is reduced, deterioration of the combustion apparatus can be prevented. Furthermore, when used as an edible, it can be a health oil.

  The microorganism that produces the enzyme is a Gram-positive bacillus, commonly called Bacillus midousuji, and is a thermophilic bacterium with an optimum growth temperature of 65 ° C. In 1995, when cryopreservation was started at Columbia University and Jikei University in the United States and a close relationship was established with the base sequence of 16S ribosomal RNA, the reference strain was 97% homologous to Geobacillus thermodenitrificans. The split time was 6.9 to 7.6 minutes. The crude enzyme obtained from Bacillus midousuji, commonly called Bacillus midousuji, was freshly cultured on trypticase soy agar medium (BBL) at 65 ° C. for 3 hours, and then re-applied to the same medium after re-applying to the same medium. Bacteria were collected, lyophilized after ultrasonic crushing, and finely pulverized with milk dust. An inexpensive corn steep liquor may be used when preparing a large amount of a crude enzyme obtained from the so-called Bacillus midousuji.

  The action of the crude enzyme obtained from the so-called Bacillus midousuji is described. When the substrate is a benzene ring bicyclic structure, an intermediate metabolite that appears to be a hydropathic glutathione-S-transferase-like enzyme using glutathione to add sulfur to hydrophilization and reductively cleave the benzene ring is observed. This is a state in which an ether bond connecting two rings is cut. It is expected that the ether bond between glycerol and fatty acid will be cleaved, and triglyceride alcholysis and fatty acid will be monoalkyl esterified.

  The biomolecule cutting action by microwave will be described. Phenomenon in which genome DNA, extranuclear DNA, RNA, protein and other biopolymers are cleaved by microwave irradiation of living organisms such as virus particles, bacteria, spore bacteria, fungi, spores and seeds under dry conditions I found. The microwave is an electromagnetic wave having a wavelength of 30 cm-0.3 mm and a frequency of 1 GHz-1 THz. In the classification based on the frequency of radio waves in the international unit system, the microwave includes a part of a decimeter wave, a part of a centimeter wave, a millimeter wave, and a submillimeter wave. In an insulator, which is a so-called pure dielectric, no current flows because electrons are confined in atoms or molecules, but vibrates when an alternating electric field is applied. This is explained as follows. In each atom or molecule constituting the dielectric material, the “electric dipole” in which the center of the distribution of the negative charge (electron) and the distribution of the positive charge (positive ion) paired with it is shifted, Each attempts to align the direction according to the direction of the electric field applied from the outside, but as the frequency increases, it becomes unable to follow, and the bonds between atoms within the molecule are broken by the friction between the molecules due to vibration and rotation. This energy loss is “dielectric loss”. The device consists of a microwave oscillator and an “applicator” such as a container, waveguide, antenna, etc. surrounded by a metal wall for placing and irradiating a heated material. The part of the mirror is randomly cut by the microwave irradiation.

  Palm oil is an example of a fat that has a reduced molecular weight, lowers the pour point, and reduces the degree of oxidation. Palm oil has a large and stable production volume worldwide and is inexpensive. Palm oil is used as an additive for foods. However, as is generally known in tropical oils, there is a concern that the pour point is as high as 12 ° C. and carcinogenic promoter activity on human cells. Cleavage the ether bond of fats and oils such as triglycerides, lowering the pour point to monoglycerides and fatty acid molecules, reducing the degree of oxidation because it is done reductively, high content of saturated fatty acids, suppressing carcinogenic promoter activity, It can be converted into health food, and excellent fuel can be manufactured at low cost.

  In the present invention, a crude enzyme obtained from the so-called Bacillus midousuji can be used, but an aldehyde group or a hydroxyl group may be added to more efficiently cleave the ether bond between glycerin and fatty acid. Although activity is observed even at room temperature, the reaction rate is fast when the reaction is carried out in a temperature range of 60 ° C. or higher because it is a thermophilic bacterium.

  The ratio of the crude enzyme obtained from the so-called Bacillus midousuji to the substrate may be about 1/1000. Save volume by reaction temperature and time. Two sections of 1 mL of palm oil in a glass container were prepared, and the crude enzyme obtained from the so-called Bacillus midousuji was used in 1/1000 (0.1%) in a quantitative ratio, and the treatment time was ( 1) 24 hours, (2) 72 hours, and the reaction temperature was 65 ° C. The control was non-enzyme added. The palm oil after reaction was left still in a 4 degreeC refrigerator, and the fluid state was observed. Observation result (1) It was confirmed that the solidification time at 10 ° C. was significantly delayed in the crude enzyme reaction zone for 24 hours compared to the non-reaction zone, and compared with 20 minutes in the crude enzyme reaction zone, It was 10 minutes in the unreacted compartment. Observation result (2) It was observed that the solidification time at 10 ° C. was further extended in the 72-hour crude enzyme reaction zone as compared to the non-reaction zone. In contrast to the fact that solidification was not observed in 18 hours in the microwave irradiation section, solidification was confirmed in 10 minutes in the non-microwave irradiation section. The frequency of the microwave that can be used in the present invention is 100 MHz to 100 GHz, and more preferably 100 MHz to 10 GHz. A method of adding an irregular molecular substance (electric dipole) that coordinates directly to the hydrocarbon molecule is also conceivable in order to cleave the hydrocarbon side chain found in the fatty acid molecule in the oil and fat more efficiently.

  The microwave irradiation time is preferably 15 minutes to 20 minutes or more. If it is within 15 minutes, the fatty acid bonded to the glycerin molecule cannot sufficiently absorb the electromagnetic wave, so that the vibration of the irregular molecule cannot be obtained, so that the hydrocarbon side chain of the fatty acid is not cleaved.

  When performing microwave irradiation intermittently, since the temperature rise by the water vapor | steam in an apparatus and the temperature rise in an apparatus by the heating of the antenna part of an electromagnetic wave irradiation apparatus are seen, it carries out, cooling the whole apparatus. For example, irradiation is performed for 15 minutes to 20 minutes, and repeated for 15 minutes to 20 minutes while observing the temperature rise of the oil.

  Prepare 2 sections of 1 mL of palm oil in a glass container, and use a 1000 W microwave generator (RE-SD50-S manufactured by Sharp Corporation). Processing time is (1) 20 minutes, (2) 40 minutes did. 2. 45 GHz microwave was irradiated. The palm oil after microwave irradiation was left still in a 10 degreeC refrigerator, and the fluid state was observed. With respect to the temperature rise of palm oil accompanying the temperature rise in the apparatus, the glass container was appropriately placed in a freezer and cooled. The observation results were as follows: (1) It was confirmed that the solidification time at 10 ° C. was significantly delayed in the microwave irradiation section for 20 minutes, compared with 20 minutes in the microwave irradiation section. In contrast, the non-microwave irradiation section was 10 minutes. Observation result (2) It was observed that the solidification time at 10 ° C. was further extended in the microwave irradiation section for 40 minutes as compared with the non-microwave irradiation section. In contrast to the fact that solidification was not observed in 18 hours in the microwave irradiation section, solidification was confirmed in 10 minutes in the non-microwave irradiation section.

  Under the same conditions, the pour point is observed to drop as shown in Table 1 in the combination of the crude enzyme obtained from the so-called Bacillus midousuji, microwave, and ethanol addition (10%). It was.

  When the chain structure of fatty acid molecules constituting fats and oils is eaten as medium chain or higher, human cells that have undergone an initiation action with carcinogens may have the effect of promoting canceration as a carcinogenic promoter. It has been reported. Therefore, it is necessary to make the fatty acid molecular structure of fats and oils as small as possible to lower the pour point, increase the saturated fatty acid content, and lower the tumor promoter activity.

  Palm oil is a vegetable oil that is solid at room temperature and contains a large amount of palmitic acid, which is a saturated fatty acid. Conventionally, palm oil has been refrigerated and purified by boiling, so that there is a problem that fatty acid is oxidized and toxic, and carcinogenic promoter activity remains as it is. Palm oil is an orange-colored oil that is solid at room temperature and has a unique aroma and sweetness. The main components are palmitic acid, oleic acid, linoleic acid, stearic acid, and myristic acid described above. The orange color of palm oil is derived from beta-carotene, and the original palm oil is rich in beta-carotene. Conventionally, retinoic acid, vitamin A, coenzyme Q10 and the like are lost because the original palm oil is boiled in the purification stage, and the color becomes white. In the method of using the crude enzyme obtained from the so-called Bacillus midousuji which is the present invention, the main component as a health oil remains as it is because it is reacted at a low temperature, and the fatty acid is non-oxidatively cleaved in a linear structure. Therefore, oils and fats reduce health and carcinogenic promoter activity and become health oils.

  The pour point of earth-friendly plant-derived fats and oils such as palm oil is lowered and the degree of oxidation is enzymatically reduced, so the content of saturated fatty acids is high, and an excellent fuel with reduced environmental burden can be produced at low cost. In addition, since the reaction is carried out at a low temperature using a crude enzyme obtained from the so-called Bacillus midousuji, the main components as health oil remain, and the fatty acid is non-oxidatively cleaved in a linear structure. Therefore, it becomes easy to produce health oil with reduced toxicity and carcinogenic promoter activity.

Claims (4)

  A method for producing fermented oil, which uses the enzymes of Bacillus midousuji (ATCC accession No. 202050) and its mutants to reductively cleave fats and oils into fatty acids and glycerin to monoalkylate and lower the pour point.   A method for producing health oil that uses the enzymes of Bacillus midousuji (ATCC accession No. 202050) and its mutants to reductively cleave fats and oils into fatty acids and glycerin to monoalkylate and lower the pour point.   An oil production method in which a microwave is irradiated to cut fatty acid side chains of fats and oils to lower the pour point.   An oil production method in which bioethanol is mixed with oil to reduce the pour point.