CN105802730B - Method for deacidifying rice bran oil by enzyme method - Google Patents

Method for deacidifying rice bran oil by enzyme method Download PDF

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Publication number
CN105802730B
CN105802730B CN201610317133.0A CN201610317133A CN105802730B CN 105802730 B CN105802730 B CN 105802730B CN 201610317133 A CN201610317133 A CN 201610317133A CN 105802730 B CN105802730 B CN 105802730B
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rice bran
bran oil
oil
lipase
deacidification
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CN105802730A (en
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邹孝强
金青哲
王兴国
黄健花
刘睿杰
常明
王小三
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Jilin Province Black Soil Cold Land Agricultural Development Co.,Ltd.
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Jiangnan University
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00Refining fats or fatty oils
    • C11B3/003Refining fats or fatty oils by enzymes or microorganisms, living or dead

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  • Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Biochemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
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Abstract

The invention discloses an enzymatic deacidification method of rice bran oil, which comprises the steps of mixing rice bran oil with glycerol, adding lipase accounting for 2-7% of the total mass of a substrate, reacting in a vacuum device for 5-7 hours, feeding a product into a nitrogen cooling device, cooling to 25-30 ℃, and centrifuging to remove the lipase to obtain the deacidified rice bran oil. The rice bran oil deacidification method by the rice bran oil enzyme method provided by the invention has the advantages of low acid value, high nutrient element retention rate and high-efficiency and rapid reaction, and is a green rice bran oil deacidification method which can be popularized in industrial production.

Description

Method for deacidifying rice bran oil by enzyme method
Technical Field
The invention belongs to the technical field of synthesis of structural glyceride, and particularly relates to an enzymatic deacidification method of rice bran oil.
Background
The rice bran oil is a vegetable oil prepared from rice bran which is a byproduct generated in rice processing, has a fatty acid composition ratio suitable for being absorbed by a human body, contains rich nutrient substances (oryzanol, vitamin E, sterol and the like), and is a nutrient health-care oil recognized in the world. Due to the lipolytic enzyme contained in rice bran, fats in rice bran are decomposed into fatty acids during rice processing and rice bran oil production, resulting in a processed raw rice bran oil containing high Free Fatty Acids (FFA), sometimes up to 40%. The traditional alkali refining deacidification and physical refining have certain limitations and are not suitable for deacidification of rice bran oil with high acid value. The prior deacidification method comprises a chemical method and a biological enzyme method, wherein a chemical catalyst has certain toxicity, the energy consumption is high, a plurality of byproducts are generated, the color of the reacted oil is deepened, and the produced oil is difficult to be used for edible oil; the enzyme catalyst has the advantages of mild condition, high reaction selectivity, high catalytic efficiency, environment-friendly product, greatly reduced cost by recycling the enzyme, and good application prospect.
The rice bran oil is vegetable oil with great nutritive value, and has reasonable fatty acid composition, unsaturated fatty acid content as high as 80%, saturated fatty acid content as high as 15-20% and long carbon chain fatty acid content over eighteen carbon atoms. The content of oleic acid and linoleic acid in the rice bran oil is respectively about 42 percent and 38 percent, and the proportion of the oleic acid and the linoleic acid is close to that recommended by the World Health Organization (WHO) 1: 1 proportion, and the rice bran oil also contains rich nutrient substances such as tocotrienol, squalene, oryzanol and the like. Because the rice bran contains lipase which has strong activity and can rapidly hydrolyze rice bran lipid, the acid value of the crude oil is rapidly increased, so that the acid value of the rice bran crude oil is high, about 10-30 mgKOH/g, and some of the acid values are even higher, which brings great difficulty to the refining of the rice bran oil. The raw rice bran oil also contains 3 to 5 percent of wax, phospholipid, pigment and other impurities, which can be removed only by refining, but the refining causes the loss of nutrient components, and particularly the deacidification process plays a decisive role in the retention of the nutrient components.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above and/or other problems occurring in the prior art enzymatic deacidification of rice bran oil.
Therefore, one of the purposes of the invention is to overcome the defects of the conventional chemical method and the enzymatic deacidification method, and provide the enzymatic deacidification method for the deacidified rice bran oil with low acid value, high oryzanol retention rate and lipase recoverability by utilizing the high efficiency and specificity of the enzymatic reaction.
To solve the above technical problem, according to an aspect of the present invention, the present invention provides the following technical solutions: a method for deacidifying rice bran oil by an enzyme method comprises the steps of mixing rice bran oil with glycerol, adding lipase accounting for 2% -7% of the total mass of a substrate, reacting for 5-7 hours in a vacuum device, sending a product into a nitrogen cooling device, cooling to 25-30 ℃, and removing the lipase by centrifugation to obtain the deacidified rice bran oil.
As a preferable scheme of the rice bran oil deacidification method by the enzyme method, the rice bran oil deacidification method comprises the following steps: the rice bran oil is subjected to pretreatment and degumming and dewaxing processes, the phospholipid content is below 10mg/kg, the wax content is below 1000mg/kg, and the acid value is 20-90 mgKOH/g.
As a preferable scheme of the rice bran oil deacidification method by the enzyme method, the rice bran oil deacidification method comprises the following steps: the addition amount of the glycerol accounts for 30-35% of FFA in the rice bran oil in mass fraction based on the weight of the rice bran oil.
As a preferable scheme of the rice bran oil deacidification method by the enzyme method, the rice bran oil deacidification method comprises the following steps: the lipase is Lipozyme 435 lipase.
As a preferable scheme of the rice bran oil deacidification method by the enzyme method, the rice bran oil deacidification method comprises the following steps: the reaction in the vacuum device is carried out in the vacuum device at the reaction temperature of 40-80 ℃ and the vacuum degree of 40-60 mbar.
As a preferable scheme of the rice bran oil deacidification method by the enzyme method, the rice bran oil deacidification method comprises the following steps: the nitrogen cooling device has the device temperature of 3-7 ℃, the nitrogen purity of 99.99%, the gas speed of 0.8-1.2 m/s and the cooling speed of 12-15 ℃/h.
As a preferable scheme of the rice bran oil deacidification method by the enzyme method, the rice bran oil deacidification method comprises the following steps: the pretreatment is that the rice is treated by high-temperature high-pressure steam, the temperature is raised to 105-115 ℃, and then the high temperature and the high pressure are kept for 5-10 min; and then cooling to 45-55 ℃, drying for 25-35 min by hot air at 35-45 ℃, and reducing the water content to 7-9% by mass.
After the enzymatic deacidification reaction is finished, the temperature of the product is generally 40-80 ℃, and the product is high in temperature, so that the viscosity of the system is high, and the separation is not facilitated. Therefore, the nitrogen cooling device is used for cooling the waste water to 25-30 ℃, and the separation effect and efficiency are greatly improved. Meanwhile, nitrogen is introduced to avoid oxidation of the rice bran oil after deacidification by an enzyme method, so that the quality of the rice bran oil is improved.
The invention has the following beneficial effects: the rice bran oil deacidification method by the enzyme method utilizes the high efficiency and specificity of enzyme reaction, and the acid value of the obtained rice bran oil can be as low as 1.96 mgKOH/g; the reaction condition is mild, the nutrient elements in the rice bran oil are greatly reserved, and the oryzanol retention rate can reach 87.9%; the liquid lipase can be recycled after reaction, thereby greatly reducing the process cost. Therefore, the rice bran oil deacidification method provided by the invention is efficient and rapid, conforms to green chemistry, and is convenient for industrial production.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1:
mixing 500g of rice bran oil with phospholipid content of 8.0mg/kg, wax content of 502mg/kg and acid value of more than 26.8mg KOH/g with glycerol, wherein the mass fraction of the glycerol accounting for the weight of the rice bran oil is 33 percent of FFA in the rice bran oil, adding Lipozyme 435 lipase accounting for 3 percent of the total mass of a substrate, reacting for 6 hours in a vacuum device, sending a product into a nitrogen cooling device, cooling to 25 ℃, centrifuging the product at the speed of 2500rpm for 6 minutes, taking an oil phase, and centrifuging at the speed of 3500rpm for 8 minutes to obtain the deacidified rice bran oil. It was found that the acid value of rice bran oil was 1.96mgKOH/g and the oryzanol retention was 87.9%.
Example 2:
mixing 500g of rice bran oil with phospholipid content of 4.8mg/kg, wax content of 609mg/kg and acid value of more than 39.6mg KOH/g with glycerol, wherein the mass fraction of the glycerol accounting for the weight of the rice bran oil is 33 percent of FFA in the rice bran oil, adding Lipozyme 435 lipase accounting for 3 percent of the total mass of a substrate, reacting for 6 hours in a vacuum device, sending a product into a nitrogen cooling device, cooling to 25 ℃, centrifuging the product at the speed of 2500rpm for 6 minutes, taking an oil phase, and centrifuging at the speed of 3500rpm for 8 minutes to obtain the deacidified rice bran oil. It was found that the acid value of rice bran oil was 3.03mgKOH/g and the oryzanol retention was 85.6%.
Example 3:
mixing 500g of rice bran oil with phospholipid content of 3.9mg/kg, wax content of 302mg/kg and acid value of more than 62.8mg KOH/g with glycerol, wherein the mass fraction of the glycerol accounting for the weight of the rice bran oil is 33 percent of FFA in the rice bran oil, adding Lipozyme 435 lipase accounting for 3 percent of the total mass of a substrate, reacting for 6 hours in a vacuum device, sending a product into a nitrogen cooling device, cooling to 25 ℃, centrifuging the product at the speed of 2500rpm for 6 minutes, taking an oil phase, and centrifuging at the speed of 3500rpm for 8 minutes to obtain the deacidified rice bran oil. It was found that the acid value of rice bran oil was 3.92mgKOH/g and the oryzanol retention was 85.6%.
Example 4:
crushing 0.5kg of rice in a crusher, sieving the crushed rice with a 50-mesh sieve, immediately placing the rice powder in a container, uniformly spreading a layer of the rice powder to uniformly distribute the powder, then placing the container in an autoclave, setting the temperature to be 105 ℃ for 5min, taking out the rice powder, cooling the rice powder to 45 ℃, drying the rice powder for 25min by hot air at 35 ℃, reducing the water content to 7% by mass, and then carrying out degumming and dewaxing processing to obtain the rice bran oil. Mixing 500g of rice bran oil with phospholipid content of 3.9mg/kg, wax content of 302mg/kg and acid value of more than 62.8mgKOH/g with glycerol, wherein the mass fraction of the glycerol accounting for the weight of the rice bran oil is 33 percent of FFA in the rice bran oil, adding Lipozyme 435 lipase accounting for 3 percent of the total mass of a substrate, reacting for 6 hours in a vacuum device, sending a product into a nitrogen cooling device, cooling to 25 ℃, centrifuging the product at the speed of 2500rpm for 6 minutes, taking an oil phase, and centrifuging at the speed of 3500rpm for 8 minutes to obtain the deacidified rice bran oil. It was found that the acid value of rice bran oil was 2.12mgKOH/g and the oryzanol retention was 88.9%.
Therefore, compared with the conventional deacidification method, the method has the advantages that the reaction efficiency is high, the deacidification effect is good, and the acid value of the obtained rice bran oil can reach 1.96 mgKOH/g; the reaction condition is mild, the nutrient elements in the rice bran oil are greatly reserved, and the oryzanol retention rate can reach 87.9%; the recovery rate of the liquid lipase enzyme protein and the recovery rate of the enzyme activity which are recovered after the reaction are both high, and the liquid lipase enzyme protein and the enzyme activity can be repeatedly utilized for many times, so that the process cost is greatly reduced. Therefore, the rice bran oil deacidification method provided by the invention is efficient and rapid, meets the requirements of green chemistry and is convenient for industrial production.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.

Claims (1)

1. A rice bran oil deacidification method by an enzyme method is characterized in that:
mixing rice bran oil and glycerol, adding lipase 3% of the total mass of the substrate, reacting in a vacuum device for 6h, feeding the product into a nitrogen cooling device at 5 ℃, cooling to 25 ℃, centrifuging the product at 2500rpm for 6min, centrifuging the oil phase at 3500rpm for 8min to obtain deacidified rice bran oil, wherein,
the lipase is Lipozyme 435 lipase;
the rice bran oil is rice bran oil which is subjected to pretreatment and degumming and dewaxing processes, the phospholipid content is 3.9mg/kg, the wax content is 302mg/kg, and the acid value is more than 62.8 mgKOH/g;
the mass fraction of the glycerol addition amount in the rice bran oil is 33 percent of FFA in the rice bran oil;
the reaction in the vacuum device is carried out in the vacuum device at the reaction temperature of 40-80 ℃ and the vacuum degree of 40-60 mbar;
the nitrogen cooling device has the nitrogen purity of 99.99 percent, the gas speed of 1m/s and the cooling speed of 15 ℃/h.
CN201610317133.0A 2016-05-15 2016-05-15 Method for deacidifying rice bran oil by enzyme method Active CN105802730B (en)

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CN109837135A (en) * 2017-11-28 2019-06-04 中国科学院青岛生物能源与过程研究所 A kind of method of the rice bran oil enzyme process depickling of ultrasonic wave added

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101974575A (en) * 2010-10-28 2011-02-16 江南大学 Preparation method of rice bran oil rich in diacylglycerol
CN104774686A (en) * 2015-03-20 2015-07-15 武汉轻工大学 Enzyme-method esterification deacidification technology for rice bran oil with high acid value

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101974575A (en) * 2010-10-28 2011-02-16 江南大学 Preparation method of rice bran oil rich in diacylglycerol
CN104774686A (en) * 2015-03-20 2015-07-15 武汉轻工大学 Enzyme-method esterification deacidification technology for rice bran oil with high acid value

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Patentee after: Jilin Province Black Soil Cold Land Agricultural Development Co.,Ltd.

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