WO2016037451A1 - 一种多不饱和脂肪酸的固定床脱色工艺 - Google Patents

一种多不饱和脂肪酸的固定床脱色工艺 Download PDF

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WO2016037451A1
WO2016037451A1 PCT/CN2015/000637 CN2015000637W WO2016037451A1 WO 2016037451 A1 WO2016037451 A1 WO 2016037451A1 CN 2015000637 W CN2015000637 W CN 2015000637W WO 2016037451 A1 WO2016037451 A1 WO 2016037451A1
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polyunsaturated fatty
fatty acid
fixed bed
solvent
methyl
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PCT/CN2015/000637
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English (en)
French (fr)
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项学兵
许新德
邵斌
李冲
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浙江医药股份有限公司新昌制药厂
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Priority to US15/509,856 priority Critical patent/US20170251705A1/en
Priority to EP15840668.6A priority patent/EP3202876B1/en
Publication of WO2016037451A1 publication Critical patent/WO2016037451A1/zh

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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/40—Colouring or decolouring of foods
    • A23L5/49—Removing colour by chemical reaction, e.g. bleaching
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, 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
    • C11B3/00—Refining fats or fatty oils
    • C11B3/10—Refining fats or fatty oils by adsorption
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/115—Fatty acids or derivatives thereof; Fats or oils
    • A23L33/12—Fatty acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, 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
    • C11B3/00—Refining fats or fatty oils
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • the invention mainly describes a decolorization process of a polyunsaturated fatty acid fixed bed. Specifically, the invention selects a fixed bed of a filler to decolorize the polyunsaturated fatty acid raw material, and directly recycles the raw material through a fixed bed or in a fixed bed.
  • the process has no effect on the quality of polyunsaturated fatty acids other than color, suitable for including fish oil (directly extracted omega-3 polyunsaturated fatty acids), algae Decolorization operation of a mixture of one or more polyunsaturated fatty acids of oil (fermented omega-3 polyunsaturated fatty acid), linoleic acid, conjugated linoleic acid, linolenic acid, arachidonic acid, and the like.
  • fish oil directly extracted omega-3 polyunsaturated fatty acids
  • algae Decolorization operation of a mixture of one or more polyunsaturated fatty acids of oil (fermented omega-3 polyunsaturated fatty acid), linoleic acid, conjugated linoleic acid, linolenic acid, arachidonic acid, and the like.
  • Polyunsaturated fatty acids are important material basis for the metabolism of the body, especially in infants and young children. They are the constituents of cell membranes, mainly to maintain cell membrane fluidity, promote cholesterol esterification, lower cholesterol and triglycerides. It reduces blood viscosity, improves blood circulation and other physiological functions, and also has the functions of improving human thinking and enhancing memory.
  • the human body cannot synthesize polyunsaturated fatty acid (PUFA) substances, and must pass Ingested by eating, etc.
  • PUFAs polyunsaturated fatty acids
  • omega-3 polyunsaturated fatty acids PUFA
  • omega-6 polyunsaturated fatty acids PUFA
  • PUFA omega-6 polyunsaturated fatty acids
  • PUFA ⁇ -9 polyunsaturated Fatty acid
  • PUFA ⁇ -9PUFA
  • ⁇ -linolenic acid ALA
  • EPA eicosapentaenoate
  • DHA docosahexaenoic acid
  • DPA docosapentaenoic acid
  • LA linoleic acid
  • CLA conjugated linoleic acid
  • GLA ⁇ -linolenic acid
  • arachidonic acid AA
  • Polyunsaturated fatty acids are mainly derived from algae extracts and aquatic animal oils.
  • One important source is fish oil. Since the polyunsaturated fatty acid raw material is basically derived from the extract, the product contains some pigments and other colored impurities, among which a small amount of impurities are harmful to the body, industrially producing polyunsaturated fatty acid related products, and the final product standard has certain color to the product. The requirement is that the colorless to pale yellow transparent liquid, so the process of industrial preparation of polyunsaturated fatty acid products basically includes a decolorization process.
  • the decolorizing agent used in the industrial decolorization process includes activated carbon, diatomaceous earth, clay, silica gel or ion exchange resin, and the widely used methods generally have a kettle-type stirring decolorization process, that is, under certain conditions, the polyunsaturated The fatty acid product is stirred with the decolorizing agent, mixed for a suitable period of time, directly filtered and recovered, and finally a polyunsaturated fatty acid product is obtained.
  • the process has the following disadvantages: 1) Process part of the process, open operation, raw materials or intermediates with air or oxygen Contact, resulting in product oxidation damage, product quality decline; 2) process is intermittent operation, industrial design and large-scale production has certain difficulties; 3) decolorant is more difficult to recycle; 4) difficult to deal with decolorizer; 5) bleaching The entrained part of the agent is difficult to recover due to the difficulty in recycling, and the process yield is reduced; 6) the process operation is complicated; 7) the environmental pollution problem caused by the process and the safety problem are large.
  • the decolorizing agent is adsorbed to a certain amount of polyunsaturated fatty acid products after use, and the recovery is difficult, resulting in a large loss of polyunsaturated fatty acids, which has a great influence on the yield.
  • the open treatment process of these decolorizing agents in the production operation has a large pollution to the surrounding environment, and the open treatment such as activated carbon is more likely to cause fire and has a large safety hazard.
  • the above-mentioned multi-unsaturated fatty acid raw material tank-type stirring decolorization process itself has many insurmountable defects, and it is difficult to adapt to large-scale industrial production.
  • the decolorization process now has some research on the choice of the process implementation, among which the majority of the existing processes use the kettle-type stirring decolorization to a certain extent to achieve the final decolorization purpose. But can not overcome or improve the above deficiencies.
  • Fixed bed technology has certain uses in other aspects of the industry, such as fixing Bed technology has more use in product separation, which can achieve better separation effect. Compared with traditional processes such as kettle agitation, the advantages are very obvious.
  • the fixed bed equipment mainly fixes a special packing in the fixed bed equipment, and the fluid or liquid material such as liquid or gas directly passes through the packing in the fixed bed or in the packing in the fixed bed, and finally reaches the adsorption of the material by the filler.
  • the purpose of separation has many advantages such as high efficiency, environmental protection, energy saving.
  • the invention mainly describes a decolorization process. Specifically, the invention creatively selects a fixed bed of a filler to decolorize a solution of a polyunsaturated fatty acid raw material or a polyunsaturated fatty acid raw material, and directly passes the material through a fixed bed or in a fixed bed. The cycle achieves the purpose of decolorization, and finally a colorless or light colored polyunsaturated fatty acid product is obtained.
  • the fixed bed decolorization process comprises: 1) filling a fixed bed filler in a decolorized fixed bed, and completely purging the decolorized fixed bed using a dissolving solvent; The polyunsaturated fatty acid material or the polyunsaturated fatty acid solution is rinsed to the decolorized fixed bed 1-2 times to obtain a stable decolorization fixed bed device; wherein: the polyunsaturated fatty acid solution comprises the polyunsaturated fatty acid material and Dissolving the solvent; 2) uniformly mixing the polyunsaturated fatty acid starting material or the polyunsaturated fatty acid solution with the dissolving solvent to obtain a mixed solution; and 3) passing the mixed solution through the decolorizing fixed bed
  • the feed port is fed, and the mixed liquid is directly discharged through the discharge port of the decolorization fixed bed, and the fixed bed temperature is 0-150 ° C to obtain a decolorized mixed solution, and the solvent is recovered under reduced pressure to
  • Polyunsaturated fatty acid product wherein: the polyunsaturated fatty acid raw material is selected from the group consisting of free polyunsaturated fatty acids and methyl esters And a group consisting of a fatty acid, an ethyl ester type polyunsaturated fatty acid, and a glyceride type polyunsaturated fatty acid; the fixed bed filler is selected from the group consisting of activated carbon, diatomaceous earth, clay, silica gel, ion exchange resin;
  • the invention includes an alkane organic solvent, an ester organic solvent, an alcohol organic solvent, an ether organic solvent, and a ketone organic solvent.
  • the polyunsaturated fatty acid raw material in the present invention comprises one or more polyunsaturated fatty acids such as free polyunsaturated fatty acid, methyl ester polyunsaturated fatty acid, ethyl ester polyunsaturated fatty acid, glyceride polyunsaturated fatty acid and the like. mixture.
  • the total content of polyunsaturated fatty acids in the polyunsaturated fatty acid raw material is 10 to 100 wt.%.
  • the polyunsaturated fatty acids described in the present invention include various contents of fish oil (directly extracted various types of omega-3 polyunsaturated fatty acids), algae oil (fermentation-derived various types of omega-3 polyunsaturated fatty acids), linoleic acid, A mixture of one or more polyunsaturated fatty acids of one or more of conjugated linoleic acid, linolenic acid, and arachidonic acid.
  • the activated carbon in the filler in the fixed bed of the present invention comprises one or a mixture of powdered activated carbon, granular activated carbon, amorphous granular activated carbon, cylindrical activated carbon, spherical activated carbon and the like.
  • Diatomaceous earth is various types of diatomaceous earth.
  • the clay is various types of clay.
  • the silica gel comprises one or a mixture of macroporous silica gel, coarse pore silica gel, B silica gel, fine pore silica gel, and the like.
  • the ion exchange resin includes one or a mixture of a neutral ion exchange resin, a weakly acidic ion exchange resin, a weakly basic ion exchange resin, and the like.
  • the feed method of the polyunsaturated fatty acid raw material in the present invention through the decolorization fixed bed comprises an upper feed, an intermediate feed and a bottom feed; and the discharge mode of the polyunsaturated fatty acid raw material through the decolorized fixed bed Includes upper discharge or intermediate discharge and bottom discharge.
  • the decolorization fixed bed has an aspect ratio of 1:1 to 1:20.
  • the solvent used in the solution of the polyunsaturated fatty acid raw material in the present invention includes an alkane Organic solvents such as hydrocarbons, esters, alcohols, ethers, and ketones.
  • the alkane solvent includes n-hexane, cyclohexane, n-heptane, octane, decane, decane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2-methyl Pentane, 3-methylpentane, 2,2,4-trimethylpentane, 2,3,4-trimethylpentane, 2,2,3-trimethylpentane, 2,2, One or a mixture of 5-trimethylhexane, heptane isomers, and the like.
  • the ester solvent includes methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, acetic acid.
  • the ether solvent includes diethyl ether, propyl ether, diisopropyl ether, dibutyl ether, pentyl ether, isoamyl ether, methyl ethyl ether, methyl propyl ether, methyl n-butyl ether, ethyl butyl ether, One or a mixture of methyl tert-butyl ether, ethyl tert-butyl ether, anisole, phenethyl ether, butylphenyl ether, amyl phenyl ether, and the like.
  • the ketone solvent includes one or a mixture of acetone, methyl ethyl ketone, methyl acetone, 2-pentanone, 3-pentanone, 3-methyl-2-butanone or the like.
  • the alcohol solvent includes methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, 2-methyl-1-butanol, isoamyl alcohol, secondary One or a mixture of pentanol, 3-pentanol, tert-amyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, and the like.
  • the concentration of the polyunsaturated fatty acid raw material is over-diluted to further reduce the damage such as oxidation, and on the other hand, it is beneficial to improve the flow rate and uniform distribution of the material in the fixed bed, and facilitate the control of the process.
  • the weight of the dissolving solvent added to the polyunsaturated fatty acid solution in the process of the present invention is 0.1 to 10 times the weight of the polyunsaturated fatty acid starting material.
  • the temperature is controlled from 0 to 150 ° C, on the one hand to improve the process conditions to achieve the best decolorization effect, and on the other hand to improve the viscosity of the material and the flow rate of the material in the fixed bed.
  • the filler in the fixed bed can be directly reused, that is, the decolorization process can be repeated, and the effect on the decolorization effect is small.
  • the filler in the fixed bed can be directly cleaned by using a cleaning solvent, and the cleaning method can adopt the same material flow direction as in the decolorization process, or can be reversed in the decolorization process.
  • the fixed bed filler cleaning solvent cleaning operation may be performed by using a single or mixed solvent, and the cleaning solvent is water or a cleaning solvent for dissolving polyunsaturated fatty acids in the above decolorizing process, and the cleaning solvent includes water and the dissolving solvent.
  • the dissolving solvent includes the solvent such as the alkane, ester, alcohol, ether, ketone or the like.
  • the alkane solvent includes n-hexane, cyclohexane, n-heptane, octane, decane, decane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2-methyl Pentane, 3-methylpentane, 2,2,4-trimethylpentane, 2,3,4-trimethylpentane, 2,2,3-trimethylpentane, 2,2, One or a mixture of 5-trimethylhexane, heptane isomers, and the like.
  • the ester solvent includes methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, acetic acid.
  • Methyl ester ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, C Isobutyl acrylate, amyl propionate, isoamyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, isobutyl butyrate, amyl butyrate, butyrate Amyl ester, methyl isobutyrate, ethyl isobutyrate, propyl isobutyrate, butyl isobutyrate, isobutyl isobutyrate, amyl isobutyrate, isoamyl isobutyrate, valerate Ester, ethyl valerate, propyl valerate, but
  • the ether solvent includes diethyl ether, propyl ether, diisopropyl ether, dibutyl ether, pentyl ether, isoamyl ether, methyl ethyl ether, methyl propyl ether, methyl n-butyl ether, ethyl butyl ether, One or a mixture of methyl tert-butyl ether, ethyl tert-butyl ether, anisole, phenethyl ether, butylphenyl ether, amyl phenyl ether, and the like.
  • the ketone solvent includes one or a mixture of acetone, methyl ethyl ketone, methyl acetone, 2-pentanone, 3-pentanone, 3-methyl-2-butanone or the like.
  • the alcohol solvent includes methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, 2-methyl-1-butanol, isoamyl alcohol, secondary One or a mixture of pentanol, 3-pentanol, tert-amyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, and the like.
  • the decolorized product or eluate obtained by the invention is subjected to appropriate treatment to finally obtain a colorless or light yellow polyunsaturated fatty acid product, which has no influence on other qualities except color, and even other products such as heavy metals and dioxins in the product.
  • Trace substances such as benzoquinone also have a certain removal effect.
  • the polyunsaturated fatty acid solution in the decolorized fixed bed is decolorized, and the solvent and the polyunsaturated fatty acid product are obtained by recovering the solvent under reduced pressure or atmospheric pressure.
  • the invention only needs to control the material flow in the production process due to the use of the fully enclosed operation. Speed and product quality monitoring, at the same time the process will not cause the risk of oxidative damage caused by the contact of materials with air or oxygen, to ensure product quality.
  • the final process produces very little waste, basically does not cause environmental pollution, and has little safety risk, which is very suitable for large-scale production.
  • the decolorizing agent in the fixed bed of polyunsaturated fatty acid of the invention adopts a fixed mode, and the modes adopted in the process and the advantages possessed include the following:
  • the process can be selected for continuous operation or batch operation. Under certain conditions, the operation process and complexity are greatly simplified, and the process is very stable.
  • the raw polyunsaturated fatty acid or polyunsaturated fatty acid solution is circulated directly through a fixed bed or in a fixed bed, wherein the feeding position includes feeding by upper or middle or bottom or mixing, upper or middle or bottom or mixing
  • the discharge ensures the maximum contact and more uniform distribution of the polyunsaturated fatty acid or its solution with the decolorizing agent, thereby achieving the best decolorization effect.
  • the decolorizing agent is recycled to eliminate the environmental pollution and safety hazards of the process.
  • the elution agent can be used for elution.
  • the elution operation is basically the same as the decolorization process. The process is simple or easy, and the elution can be put into use immediately. and many more.
  • the invention creatively selects a de-coloring of polyunsaturated fatty acid raw materials by a fixed bed process using a decolorizing agent as a filler.
  • a decolorizing agent as a filler.
  • polyunsaturated fatty acids are directly circulated through a fixed bed decolorizing agent or in a fixed bed decolorizing agent filler.
  • the process decolorization in the invention includes continuous operation or intermittent sealing operation, which simplifies the operation process and complexity, and the process is relatively stable, which improves the quality of the product to some extent, reduces or eliminates the loss of the product, and improves the product.
  • the yield of the product is fed in a simple or composite manner, so that the maximum contact and more uniform distribution of the material and the decolorizing agent can achieve the best decolorization effect, and the environmental pollution and safety hazards of the process are largely eliminated.
  • the decolorizing agent is weakened or disappeared, the eluent can be eluted with an eluent.
  • the elution operation is relatively simple and easy to operate, and the elution can be immediately put into use.
  • Figure 1 is a fixed bed of a polyunsaturated fatty acid decolorization process.
  • the fixed bed 1 is selected, wherein the fixed bed has a diameter of 0.1 m and a height of 0.5 m (a diameter to height ratio of 1:5).
  • the powdered activated carbon filler is filled in the decolorized fixed bed, and the fixed bed is completely rinsed with the solvent n-hexane, and then the fixed bed is rinsed 1 to 2 times with an appropriate amount of free fish oil raw material to obtain a stable decolorization fixed bed device, such as figure 1.
  • the above free fish oil/n-hexane solution is prepared for decolorization, and is fed through the fixed bed top feed port 3, and the bottom discharge port 2 is discharged (up and down), the material is directly discharged through the fixed bed, and no circulation is performed, and the fixed bed is not used.
  • the temperature was 30 ° C
  • the decolorization time was about 0.5 hour
  • the free fish oil/n-hexane solution after decolorization was received, and the color was pale yellow.
  • the solvent was recovered under reduced pressure to obtain 496 g of free fish oil product, and the color was pale yellow.
  • the free fish oil product was tested: EPA 17.3%, DHA 11.5%, total free polyunsaturated fatty acid content 42.0%, pale yellow color, yield 99.0%.
  • the free fish oil product was tested: EPA 17.1%, DHA 11.6%, total free polyunsaturated fatty acid content was 41.8%, color was pale yellow, yield was 91.1%.
  • Example 1 the decolorization fixed bed process of the present invention is used, and the decolorization is carried out by selecting activated carbon as a fixed bed of the filler, and the free-type fish oil various polyunsaturated fatty acid raw materials/n-hexane solution is decolorized at 30 ° C.
  • the obtained free-type fish oil product after decolorization is light in color, and the decolorization effect is better.
  • the product yield is 99.0%, the yield is high, and the other qualities except the color of the product are abnormal, and the activated carbon has direct re-use. effect.
  • the fixed bed decolorization process of the present invention can have the advantages of simple process, good decolorization effect, high yield, low cost, safety and environmental protection, and better industrial scale. The feasibility of chemical production.
  • Example 2 The decolorized fixed bed used in the above Example 1 (in which the fixed bed diameter is 0.1 m, the height is 0.5 m, the aspect ratio is 1:5, the powder type activated carbon filler, the temperature is 30 ° C), and the fixed bed is repeatedly used for repeated decolorization and utilization.
  • the results are shown in the table below.
  • the implementation objects and related parameters of Examples 3 to 15 are listed in Table 2.
  • the decolorized fixed bed used in the above Examples 16 to 20 (in which the fixed bed diameter is 0.1 m, the height is 0.5 m, the aspect ratio is 1:5, the powder type activated carbon filler, the temperature is 30 ° C), and the fixed bed is repeatedly used for repeated decolorization. Thereafter, the fixed bed was washed with a n-hexane washing solvent, and after the completion of the washing, the fixed bed was used for repeated decolorization, and the results shown in the following table were obtained.

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Abstract

一种多不饱和脂肪酸的固定床脱色工艺，包括在一定条件下，多不饱和脂肪酸或多不饱和脂肪酸溶液直接通过固定床填料或在固定床填料中循环，最终得到无色或浅色多不饱和脂肪酸产品，同时对多不饱和脂肪酸除色泽外的其他品质没有影响。脱色工艺可以进行连续操作或者间歇操作，固定床填料包括活性炭、硅藻土、白土、硅胶、离子交换树脂中一种或几种的混合物，多不饱和脂肪酸原料或多不饱和脂肪酸原料溶液采用上部或中间或底部或混合进料，固定床中填料可以反复利用，填料在脱色效果变差或失去脱色效果后可以进行清洗再重复利用。

Description

一种多不饱和脂肪酸的固定床脱色工艺 技术领域
本发明主要描述一种多不饱和脂肪酸固定床脱色工艺，具体而言，本发明创造性选用一种填料固定床对多不饱和脂肪酸原料进行脱色，将原料直接通过固定床或在固定床中循环达到脱色目的，最终得到无色或浅色多不饱和脂肪酸产品，该工艺对多不饱和脂肪酸除色泽外的其他品质没有影响，适用于包括鱼油(直接提取的ω-3多不饱和脂肪酸)、藻油(发酵来源的ω-3多不饱和脂肪酸)、亚油酸、共轭亚油酸、亚麻酸、花生四烯酸等其中一种或多种多不饱和脂肪酸的混合物的脱色操作应用。
背景技术
随着人们越来越关注自身的健康，大众开始更多的摄取营养健康膳食补充剂，多不饱和脂肪酸(PUFA)类产品在其中占有很重要的地位。
多不饱和脂肪酸(PUFA)是机体代谢，特别是婴幼儿大脑发育等活动中的重要物质基础，是细胞膜的构成成分，主要起到保持细胞膜流动性，促使胆固醇酯化，降低胆固醇和甘三酯，降低血液粘稠度，改善血液循环等生理功能，同时还具备改善人类思维和增强记忆力等作用。而人体自身无法合成多不饱和脂肪酸(PUFA)物质，必须通 过饮食等进行摄取获得。
多不饱和脂肪酸(PUFA)种类繁多，主要包括ω-3多不饱和脂肪酸(PUFA)(ω-3PUFA)、ω-6多不饱和脂肪酸(PUFA)(ω-6PUFA)、ω-9多不饱和脂肪酸(PUFA)(ω-9PUFA)等形式，如α-亚麻酸(ALA)、二十碳五烯酯(EPA)、二十二碳六烯酸(DHA)、二十二碳五烯酸(DPA)、亚油酸(LA)、共轭亚油酸(CLA)，γ-亚麻酸(GLA)、花生四烯酸(AA)等，其中尤以二十碳五烯酸(EPA)和二十二碳六烯酸(DHA)为主要代表的ω-3多不饱和脂肪酸(ω-3PUFA)最为大众所熟知和接受，对人体和动物健康具备的改善和促进作用也最明显，部分多不饱和脂肪酸物质的分子结构式如下：
Figure PCTCN2015000637-appb-000001
Figure PCTCN2015000637-appb-000002
多不饱和脂肪酸主要来源于藻类提取物和水产动物油，其中一个重要来源为鱼油。由于多不饱和脂肪酸原料基本来自提取物，所以产品中包含部分色素等有色杂质，其中少量杂质对机体有害，工业上生产多不饱和脂肪酸相关产品，最终的产品标准都对产品的色泽有一定的要求，即无色至浅黄色透明液体，所以工业制备多不饱和脂肪酸产品过程基本都包含脱色工序。
目前工业中脱色工艺使用的脱色剂包括活性炭、硅藻土、白土、硅胶或者离子交换树脂等材料，而广泛使用的方法一般都为釜式搅拌脱色工艺，即在一定条件下，将多不饱和脂肪酸产品与脱色剂一起搅拌，混合适当的时间后，直接过滤和回收，最后得到多不饱和脂肪酸产品，该工艺具有以下缺点：1)工艺部分工序开放式操作，原料或中间体与空气或氧气接触，导致产品被氧化破坏，产品质量下降；2)工艺为间歇式操作，工业设计及规模化生产具有一定的困难；3)脱色剂较难回收套用；4)脱色剂处理困难；5)脱色剂的夹带部分多不饱和脂肪酸产品难以回收导致损耗较大，工艺收率降低；6)工艺操作较为复杂；7)工艺带来的环境污染问题及安全问题较大等等。
目前有部分文献公开了相关多不饱和脂肪酸脱色工艺技术，如专利CN102994236、CN1101935、CN103525564、CN1283392、CN103540415、等介绍使用0.1～5％活性白土脱色剂对多不饱和脂肪酸进行脱色，专利CN103725403、CN1263145、CN101940240等则 选择使用活性炭作为脱色剂，还有专利CN1769409等选择硅藻土等脱色剂，专利CN101297708等则采用阳离子交换树脂脱色剂，工艺基本过程均为在一定条件下，采用釜式搅拌脱色，脱色完成后直接过滤得到多不饱和脂肪酸，工艺具有一定的脱色效果，但过滤得到的白土、活性炭、硅藻土等均具有一定的黏性，转移和投料都比较困难，无法继续直接循环套用，同时清洗等处理程序也过于复杂，比较困难，所以一般情况下都是将使用后的脱色剂直接抛弃，不进行回收或套用等。
由于以上工艺均采用间歇式釜式搅拌操作，工艺进行中存在部分工序开放式操作，多不饱和脂肪酸产品容易与空气或氧气接触，导致产品品质下降，同时间歇式工艺对工业规模化生产有一定的制约，操作过程也较为复杂，对产品品质的监控也不是很方便。
而且间歇式釜式搅拌工艺中脱色剂使用完后均吸附一定量的多不饱和脂肪酸产品，回收比较困难，导致多不饱和脂肪酸的损耗较大，对收率有较大的影响。
同时这些脱色剂在生产操作中开放式处理工序对周边环境具有较大的污染，而活性炭等开放式处理更容易起火，有较大的安全隐患。
总体而言，以上多不饱和脂肪酸原料釜式搅拌脱色工艺本身具有很多难以克服的缺陷，难于适应大规模工业化生产。
一般而言，脱色工艺除要求选择良好的脱色剂外，现在还对工艺实施的方式选择上有一定的研究，其中现有大部分工艺采用的釜式搅拌脱色虽然一定程度能够达到最终的脱色目的，但无法克服或改善上述的诸多不足。而固定床技术在工业其他方面有一定的使用，如固定 床技术在产品分离中就有较多使用，能够达到较好的分离效果，相比釜式搅拌等传统工艺，优点十分明显。
固定床设备主要是将某种特殊填料固定在固定床设备内，液体或气体等具备流动性的物料直接通过固定床内填料或在固定床内填料内循环等过程，最终达到填料对物料的吸附或分离的目的，具有高效、环保、节能等许多优点。
发明内容
本发明主要描述一种脱色工艺，具体而言，本发明创造性选用一种填料固定床对多不饱和脂肪酸原料或多不饱和脂肪酸原料的溶液进行脱色，将物料直接通过固定床或在固定床中循环达到脱色目的，最终得到无色或浅色多不饱和脂肪酸产品。
根据本发明的多不饱和脂肪酸的固定床脱色工艺，所述固定床脱色工艺包括：1)在脱色固定床中填满固定床填料，使用溶解溶剂将所述脱色固定床完全润洗；再使用多不饱和脂肪酸原料或多不饱和脂肪酸溶液润洗所述脱色固定床1～2次，以得到稳定的脱色固定床设备；其中：所述多不饱和脂肪酸溶液包括所述多不饱和脂肪酸原料和所述溶解溶剂；2)将所述多不饱和脂肪酸原料或所述多不饱和脂肪酸溶液与所述溶解溶剂均匀混合，以得到混合液；以及3)将所述混合液通过所述脱色固定床的进料口进料，所述混合液直接通过所述脱色固定床的出料口出料，固定床温度为0～150℃，以得到脱色的混合液，经减压回收溶剂，以得到脱色的多不饱和脂肪酸产品；其中：所述多不饱和脂肪酸原料选自由游离型多不饱和脂肪酸、甲酯型多不饱 和脂肪酸、乙酯型多不饱和脂肪酸、和甘油酯型多不饱和脂肪酸组成的组；所述固定床填料选自由活性炭、硅藻土、白土、硅胶、离子交换树脂组成的；所述溶解溶剂包括烷烃类有机溶剂、酯类有机溶剂、醇类有机溶剂、醚类有机溶剂、酮类有机溶剂。
本发明中多不饱和脂肪酸原料包括游离型多不饱和脂肪酸、甲酯型多不饱和脂肪酸、乙酯型多不饱和脂肪酸、甘油酯型多不饱和脂肪酸等一种或几种多不饱和脂肪酸的混合物。其中，所述多不饱和脂肪酸原料中多不饱和脂肪酸的总含量为10～100wt.％。
本发明描述中多不饱和脂肪酸包括各种含量的鱼油(直接提取的各型ω-3多不饱和脂肪酸)、藻油(发酵来源的各型ω-3多不饱和脂肪酸)、亚油酸、共轭亚油酸、亚麻酸、花生四烯酸等其中一种或多种各型多不饱和脂肪酸混合物。
本发明中固定床里的填料中的活性炭包括粉末活性炭、颗粒活性炭、不定形颗粒活性炭、圆柱形活性炭、球形活性炭等一种或几种混合物。硅藻土为各型硅藻土。所述白土为各型白土。所述硅胶包括大孔硅胶、粗孔硅胶、B型硅胶、细孔硅胶等一种或几种混合物。所述离子交换树脂包括中性离子交换树脂、弱酸性离子交换树脂、弱碱性离子交换树脂等一种或几种混合物。
本发明中所述多不饱和脂肪酸原料通过所述脱色固定床的进料方式包括上部进料、中间进料和底部进料；所述多不饱和脂肪酸原料通过所述脱色固定床的出料方式包括上部出料或、中间出料和底部出料。其中，所述脱色固定床的径高比为1∶1～1∶20。
本发明中多不饱和脂肪酸原料的溶液所使用的溶解溶剂包括烷 烃类、酯类、醇类、醚类、酮类等有机溶剂。所述烷烃类溶剂包括正己烷、环己烷、正庚烷、辛烷、壬烷、癸烷、2，2-二甲基丁烷、2，3-二甲基丁烷、2-甲基戊烷、3-甲基戊烷、2，2，4-三甲基戊烷、2，3，4-三甲基戊烷、2，2，3-三甲基戊烷、2，2，5-三甲基己烷、庚烷异构体等一种或几种混合物。所述酯类溶剂包括甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸异丙酯、甲酸丁酯、甲酸异丁酯、甲酸戊酯、甲酸异戊酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸异丁酯、乙酸戊酯、乙酸异戊酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、丙酸异丁酯、丙酸戊酯、丙酸异戊酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯、丁酸异丁酯、丁酸戊酯、丁酸异戊酯、异丁酸甲酯、异丁酸乙酯、异丁酸丙酯、异丁酸丁酯、异丁酸异丁酯、异丁酸戊酯、异丁酸异戊酯、戊酸甲酯、戊酸乙酯、戊酸丙酯、戊酸丁酯、戊酸异丁酯、戊酸戊酯、戊酸异戊酯、异戊酸甲酯、异戊酸乙酯、异戊酸丙酯、异戊酸丁酯、异戊酸异丁酯、异戊酸戊酯、异戊酸异戊酯等一种或几种混合物。所述醚类溶剂包括乙醚、丙醚、异丙醚、丁醚、戊醚、异戊醚、甲基乙基醚、甲基丙基醚、甲基正丁基醚、乙基丁基醚、甲基叔丁基醚、乙基叔丁基醚、苯甲醚、苯乙醚、丁基苯基醚、戊基苯基醚等一种或几种混合物。所述酮类溶剂包括丙酮、丁酮、甲基丙酮、2-戊酮、3-戊酮、3-甲基-2-丁酮等一种或几种混合物。所述醇类溶剂包括甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇、仲丁醇、叔丁醇、戊醇、2-甲基-1-丁醇、异戊醇、仲戊醇、3-戊醇、叔戊醇、3-甲基-2-丁醇、新戊醇等一种或几种混合物。
本发明中之所以可能使用溶液形式的物料进行脱色，一方面为通 过稀释相关多不饱和脂肪酸原料的浓度从而进一步减少氧化等破坏，另一方面有利于改善物料在固定床中的流速和均匀分布，便于工艺的控制。
本发明的工艺中所述多不饱和脂肪酸溶液中加入的所述溶解溶剂的重量为所述多不饱和脂肪酸原料的重量的0.1～10倍。
本发明的工艺中控制温度为0～150℃，一方面为改善工艺条件以达到最佳脱色效果，另一方面为改善物料黏性和物料在固定床中的流速。
本发明中固定床中填料可以进行直接反复利用，即脱色工艺操作可以重复进行，对脱色效果影响较小。
本发明中工艺在脱色效果变差或失去脱色效果后，固定床中填料可以直接使用清洗溶剂进行清洗操作，清洗方式可以采用与脱色工艺中相同的物料流动方向，也可以采用与脱色工艺中相反的物料流动方向，从而达到最佳洗脱效果。
本发明中固定床填料清洗溶剂清洗操作可以采用单一或者混合溶剂清洗，清洗溶剂为水或者上述脱色工艺中溶解多不饱和脂肪酸的清洗溶剂，所述清洗溶剂包括水以及所述溶解溶剂。所述溶解溶剂包括所述烷烃类、酯类、醇类、醚类、酮类等溶剂。所述烷烃类溶剂包括正己烷、环己烷、正庚烷、辛烷、壬烷、癸烷、2，2-二甲基丁烷、2，3-二甲基丁烷、2-甲基戊烷、3-甲基戊烷、2，2，4-三甲基戊烷、2，3，4-三甲基戊烷、2，2，3-三甲基戊烷、2，2，5-三甲基己烷、庚烷异构体等一种或几种混合物。所述酯类溶剂包括甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸异丙酯、甲酸丁酯、甲酸异丁酯、甲酸戊酯、甲酸异戊酯、乙酸 甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸异丁酯、乙酸戊酯、乙酸异戊酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、丙酸异丁酯、丙酸戊酯、丙酸异戊酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯、丁酸异丁酯、丁酸戊酯、丁酸异戊酯、异丁酸甲酯、异丁酸乙酯、异丁酸丙酯、异丁酸丁酯、异丁酸异丁酯、异丁酸戊酯、异丁酸异戊酯、戊酸甲酯、戊酸乙酯、戊酸丙酯、戊酸丁酯、戊酸异丁酯、戊酸戊酯、戊酸异戊酯、异戊酸甲酯、异戊酸乙酯、异戊酸丙酯、异戊酸丁酯、异戊酸异丁酯、异戊酸戊酯、异戊酸异戊酯等一种或几种混合物。所述醚类溶剂包括乙醚、丙醚、异丙醚、丁醚、戊醚、异戊醚、甲基乙基醚、甲基丙基醚、甲基正丁基醚、乙基丁基醚、甲基叔丁基醚、乙基叔丁基醚、苯甲醚、苯乙醚、丁基苯基醚、戊基苯基醚等一种或几种混合物。所述酮类溶剂包括丙酮、丁酮、甲基丙酮、2-戊酮、3-戊酮、3-甲基-2-丁酮等一种或几种混合物。所述醇类溶剂包括甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇、仲丁醇、叔丁醇、戊醇、2-甲基-1-丁醇、异戊醇、仲戊醇、3-戊醇、叔戊醇、3-甲基-2-丁醇、新戊醇等一种或几种混合物。
本发明得到的脱色产物或洗脱液经过适当的处理，最终得到无色或淡黄色多不饱和脂肪酸产品，对除色泽外的其他品质没有影响，甚至对于产品中的其他如重金属、二噁英、苯苪芘等微量物质也具有一定的脱除效果。
本发明的工艺中脱色固定床中所述多不饱和脂肪酸溶液脱色后经过减压或常压回收溶剂得到套用溶剂和多不饱和脂肪酸产品。
本发明由于采用全封闭式操作，生产过程中只需要控制好物料流 速和产品质量监控，同时工艺也不会造成物料与空气或氧气接触带来产品被氧化破坏的风险，保证产品品质。
最终工艺产生的废弃物很少，基本不会造成环境污染，安全风险也很小，非常适合于规模化生产。
本发明的多不饱和脂肪酸固定床中脱色剂采用固定模式，工艺中采取的模式和具备的优点包括以下几点：
1)工艺可以选择进行连续化操作或间歇式操作，在一定条件下，大大简化操作过程和复杂程度，工艺十分稳定。
2)工艺进行连续化全封闭式操作，消除空气或氧气对产品的影响，一定程度上提高产品的品质，而且采用连续化操作克服了釜式搅拌间歇操作中脱色剂对产品的夹带，大大减少或消除产品的损耗，提高产品的收率。
3)原料多不饱和脂肪酸或多不饱和脂肪酸溶液采用直接通过固定床或在固定床中循环，其中进料位置包括采用上部或中间或底部或混合等方式进料，上部或中间或底部或混合出料，保证了多不饱和脂肪酸或其溶液与脱色剂最大程度的接触和更均匀的分布，从而达到最佳脱色效果。
4)在封闭固定床环境中，脱色剂循环套用，消除工艺的环境污染和安全隐患等问题。
5)相对于釜式间歇脱色操作，脱色剂单批使用量相对增加，所以得到的产品品质大大提高。
6)对于固定床脱色操作，可以随时进行在线取样监控和检测，操作很方便简单，更加能够保证产品品质的稳定性。
7)脱色剂脱色效果减弱或消失时，可以使用洗脱剂进行洗脱，洗脱操作与脱色工艺操作上基本一致，采用顺流或者逆流，过程十分简单易行，洗脱完毕可以立即投入使用等等。
本发明技术创造性选择采用一种以脱色剂为填料的固定床工艺对多不饱和脂肪酸原料脱色，在一定条件下，多不饱和脂肪酸直接通过固定床中脱色剂或在固定床脱色剂填料中循环达到脱色目的，发明中工艺脱色包括可以进行连续操作或者间歇式密闭操作，简化了操作过程和复杂程度等，工艺比较稳定，一定程度上提高了产品的品质，减少或消除产品的损耗，提高了产品的收率，采用简单或者复合方式进料，使物料与脱色剂最大程度的接触和更均匀的分布，能够取得最佳脱色效果，而且很大程度上消除了工艺的环境污染和安全隐患问题，还有脱色剂脱色效果减弱或消失时，可以使用洗脱剂对脱色剂进行洗脱，洗脱操作比较简单和易于实现操作，洗脱完毕可以立即投入使用等等。
附图说明
图1为一种多不饱和脂肪酸脱色工艺固定床。
具体实施方式
下面用实施例来进一步说明本发明，本发明的实施例仅用于说明本发明的技术方案，并非限定本发明。
实施例1
选取固定床1，其中固定床直径为0.1m，高度0.5m(径高比1∶5)， 在脱色固定床中填满粉末型活性炭填料，先使用溶剂正己烷将固定床润洗完全，再使用适量的游离型鱼油原料润洗固定床1～2次，得到稳定的脱色固定床设备，如图1。
将500g游离型鱼油原料(EPA 17.6％，DHA 11.7％，总游离型多不饱和脂肪酸含量为42.1％，颜色橙红色)，加入500g正己烷混合均匀配置成溶液，颜色浅橙红色。
将上述游离型鱼油/正己烷溶液准备脱色，通过固定床顶部进料口3进料，底部出料口2出料(上进下出)，物料直接通过固定床出料，不进行循环，固定床温度为30℃，脱色时间约0.5小时，接收脱色后游离型鱼油/正己烷溶液，颜色淡黄色，经过减压回收溶剂得到游离型鱼油产品496g，颜色淡黄色。
脱色完毕，通过底部排空口7将物料全部排出，再使用清洗溶剂正己烷从底部进料口2和中部进料口4进料，通过隔板6，顶部出料口3出料，对固定床内填料5进行清洗，清洗完毕，通过底部排空口7将溶剂全部排出。
检测游离型鱼油产品：EPA 17.3％，DHA11.5％，总游离型多不饱和脂肪酸含量为42.0％，颜色淡黄色，收率99.0％。
比较实施例2
在反应瓶中加入500g游离型鱼油原料(EPA 17.6％，DHA 11.7％，总游离型多不饱和脂肪酸含量为42.1％，颜色橙红色)，500g正己烷，混合均匀配置成溶液，颜色浅橙红色。
再在反应瓶中加入25g粉末型活性炭，30℃条件下，搅拌脱色1.0小时，脱色完毕后，过滤出活性炭得到游离型鱼油/正己烷溶液， 颜色淡黄色，经过减压回收溶剂得到游离型鱼油产品459g，颜色浅黄色。
检测游离型鱼油产品：EPA 17.1％，DHA 11.6％，总游离型多不饱和脂肪酸含量为41.8％，颜色浅黄色，收率91.1％。
通过比较可以看出，实施例1中采用本发明脱色固定床工艺，通过选择活性炭作为填料的固定床进行脱色，30℃条件下，游离型鱼油各型多不饱和脂肪酸原料/正己烷溶液进行脱色，得到的脱色后游离型鱼油产品，颜色很浅，脱色效果较佳，产品收率99.0％，收率较高，产品除颜色外的其他品质均为出现异常，同时活性炭具有可以直接重新利用的效果。
比较实施例2，通过常规的釜式搅拌脱色工艺，相同工艺条件，5％活性炭在30℃条件下，对游离型鱼油各型多不饱和脂肪酸原料/正己烷溶液进行脱色，最后得到脱色后游离型鱼油产品，颜色较浅，脱色效果较固定床脱色效果略差，产品收率91.1％，收率较固定床脱色工艺较低，同时活性炭由于较粘，收集以及重新投料具有一定的困难，重新利用的可能性较小。
对比两种工艺的工艺过程和实验结果，可以得到本发明的固定床脱色工艺具有工艺简单，脱色效果较好，收率较高，成本较低，安全环保等优点，同时具有更好的工业规模化生产的可行性。
实施例3～15
下表中列出了实施例3～15的实施对象和相关参数。
Figure PCTCN2015000637-appb-000003
实施例16～20(脱色剂重复利用实施例)
选取上述实施例1所用脱色固定床(其中固定床直径为0.1m，高度0.5m，径高比1∶5，粉末型活性炭填料，温度30℃)，反复使用该固定床进行重复脱色利用，得到如下表所示结果。表2中列出了实施例3～15的实施对象和相关参数。
表2
Figure PCTCN2015000637-appb-000004
实施例21～22(固定床清洗后重复利用实施例)
选取上述实施例16～20所用脱色固定床(其中固定床直径为0.1m，高度0.5m，径高比1∶5，粉末型活性炭填料，温度30℃)，反复使用该固定床进行重复脱色利用后，使用正己烷清洗溶剂对固定床进行清洗，清洗完成后再使用该固定床进行重复脱色利用，得到如下表所示结果。
表3中列出了实施例3～15的实施对象和相关参数。
表3
Figure PCTCN2015000637-appb-000005
本发明通过上面的实施例进行举例说明，但是，应当理解，本发明并不限于这里所描述的特殊实例和实施方案。在这里包含这些特殊实例和实施方案的目的在于帮助本领域中的技术人员实践本发明。任何本领域中的技术人员很容易在不脱离本发明精神和范围的情况下进行进一步的改进和完善，因此本发明只受到本发明权利要求的内容和范围的限制，其意图涵盖所有包括在由附录权利要求所限定的本发明精神和范围内的备选方案和等同方案。

Claims (14)

  1. 一种多不饱和脂肪酸的固定床脱色工艺，所述固定床脱色工艺包括：
    1)在脱色固定床中填满固定床填料，使用溶解溶剂将所述脱色固定床完全润洗；再使用多不饱和脂肪酸原料或多不饱和脂肪酸溶液润洗所述脱色固定床1～2次，以得到稳定的脱色固定床设备；其中：所述多不饱和脂肪酸溶液包括所述多不饱和脂肪酸原料和所述溶解溶剂；
    2)将所述多不饱和脂肪酸原料或所述多不饱和脂肪酸溶液与所述溶解溶剂均匀混合，以得到混合液；以及
    3)将所述混合液通过所述脱色固定床的进料口进料，所述混合液直接通过所述脱色固定床的出料口出料，固定床温度为0～150℃，以得到脱色的混合液，经减压或常压回收溶剂，以得到脱色的多不饱和脂肪酸产品；
    其中：所述多不饱和脂肪酸原料选自由游离型多不饱和脂肪酸、甲酯型多不饱和脂肪酸、乙酯型多不饱和脂肪酸、和甘油酯型多不饱和脂肪酸组成的组；
    所述固定床填料选自由活性炭、硅藻土、白土、硅胶、离子交换树脂组成的组；
    所述溶解溶剂包括烷烃类溶剂、酯类溶剂、醇类溶剂、醚类溶剂、和酮类溶剂。
  2. 根据权利要求1所述的方法，其中，所述多不饱和脂肪酸选自由鱼油(直接提取的ω-3多不饱和脂肪酸)、藻油(发酵来源的ω-3多不饱和脂肪酸)、亚油酸、共轭亚油酸、亚麻酸、和花生四烯酸组成的组。
  3. 根据权利要求2所述的方法，其中，所述多不饱和脂肪酸原料中多不饱和脂肪酸的总含量为10～100wt.％。
  4. 根据权利要求1所述的方法，其中，所述活性炭选自由粉末型活性炭、颗粒型活性炭、不定形颗粒活性炭、圆柱形活性炭和球形活性炭组成的组。
  5. 根据权利要求1所述的方法，其中，所述硅胶选自由大孔硅胶、粗孔硅胶、B型硅胶和细孔硅胶组成的组。
  6. 根据权利要求1所述的方法，其中，所述离子交换树脂选自由中性离子交换树脂、弱酸性离子交换树脂和弱碱性离子交换树脂组成的组。
  7. 根据权利要求1所述的方法，其中，所述多不饱和脂肪酸原料通过所述脱色固定床的进料方式包括上部进料、中间进料和底部进料；所述多不饱和脂肪酸原料通过所述脱色固定床的出料方式包括上部出料或、中间出料和底部出料。
  8. 根据权利要求7所述的方法，其中，所述脱色固定床的径高比为1∶1～1∶20。
  9. 根据权利要求1所述的方法，其中，所述烷烃类溶剂选自由正己烷、环己烷、正庚烷、辛烷、壬烷、癸烷、2，2-二甲基丁烷、2，3- 二甲基丁烷、2-甲基戊烷、3-甲基戊烷、2，2，4-三甲基戊烷、2，3，4-三甲基戊烷、2，2，3-三甲基戊烷、2，2，5-三甲基己烷、和庚烷异构体组成的组；所述酯类溶剂选自由甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸异丙酯、甲酸丁酯、甲酸异丁酯、甲酸戊酯、甲酸异戊酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸异丁酯、乙酸戊酯、乙酸异戊酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、丙酸异丁酯、丙酸戊酯、丙酸异戊酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯、丁酸异丁酯、丁酸戊酯、丁酸异戊酯、异丁酸甲酯、异丁酸乙酯、异丁酸丙酯、异丁酸丁酯、异丁酸异丁酯、异丁酸戊酯、异丁酸异戊酯、戊酸甲酯、戊酸乙酯、戊酸丙酯、戊酸丁酯、戊酸异丁酯、戊酸戊酯、戊酸异戊酯、异戊酸甲酯、异戊酸乙酯、异戊酸丙酯、异戊酸丁酯、异戊酸异丁酯、异戊酸戊酯、异戊酸异戊酯组成的组；所述醚类溶剂选自由乙醚、丙醚、异丙醚、丁醚、戊醚、异戊醚、甲基乙基醚、甲基丙基醚、甲基正丁基醚、乙基丁基醚、甲基叔丁基醚、乙基叔丁基醚、苯甲醚、苯乙醚、丁基苯基醚、戊基苯基醚组成的组；所述酮类溶剂选自由丙酮、丁酮、甲基丙酮、2-戊酮、3-戊酮、3-甲基-2-丁酮组成的组；所述醇类溶剂选自由甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇、仲丁醇、叔丁醇、戊醇、2-甲基-1-丁醇、异戊醇、仲戊醇、3-戊醇、叔戊醇、3-甲基-2-丁醇、新戊醇组成的组。
  10. 根据权利要求1所述的方法，其中，所述多不饱和脂肪酸溶液中加入的所述溶解溶剂的重量为所述多不饱和脂肪酸原料的重量的0.1～10倍。
  11. 根据权利要求1～10任一所述的方法，其中，所述脱色固定床中填料能够进行反复利用，在脱色效果变差或失去脱色效果后能够直接进行洗脱后重复利用。
  12. 根据权利要求1～10任一所述的方法，其中，所述脱色固定床中填料能够进行反复利用，在脱色效果变差或失去脱色效果后，能够使用清洗溶剂对所述脱色固定床进行清洗，清洗后可重复利用。
  13. 根据权利要求12所述的方法，其中，所述清洗溶剂为水和所述溶解溶剂。
  14. 根据权利要求1～10任一所述的方法，其中，所述多不饱和脂肪酸溶液脱色后经过减压或常压回收溶剂得到套用溶剂和多不饱和脂肪酸产品。
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