WO2020024644A1 - Method for improving stability and safety of microbial oils and fats - Google Patents

Method for improving stability and safety of microbial oils and fats Download PDF

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Publication number
WO2020024644A1
WO2020024644A1 PCT/CN2019/086365 CN2019086365W WO2020024644A1 WO 2020024644 A1 WO2020024644 A1 WO 2020024644A1 CN 2019086365 W CN2019086365 W CN 2019086365W WO 2020024644 A1 WO2020024644 A1 WO 2020024644A1
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fats
microbial oils
safety
stability
oil
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PCT/CN2019/086365
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French (fr)
Chinese (zh)
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瞿瀚鹏
曹晟
王身健
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梁云
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Publication of WO2020024644A1 publication Critical patent/WO2020024644A1/en

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    • 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
    • C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
    • 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
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0092—Mixtures

Definitions

  • the invention relates to the field of refining microbial oils and fats, in particular to a method for improving the stability and safety of microbial oils and fats.
  • the content of polyunsaturated fatty acids in microbial oils and fats is high, the saturation of the oils and fats is low, and the stability of the microbial oils and fats is easily caused by oxidation.
  • the "iron” element is an accelerator for the oxidation reaction, which increases the oxidation rate.
  • the degumming, degreasing, decoloring, and especially deodorizing processes of fats and oils are carried out at relatively high temperatures, and high temperature and oxygen are two important factors for oxidation of fats and oils.
  • Oxygen and chlorine in water or steam will accelerate the oxidation of fats and oils during refining, increase the acid value and peroxide value of fats and oils, and increase the production of 3 chloropropionic acid.
  • Improper processing and storage devices will not only lead to oxidation of the oil, but also increase the content of plasticizer in the oil.
  • Oxidation of fats and oils is the main reason for the change in the quality of fats and oils.
  • the oil and fats industry has added antioxidants to delay the oxidation of fats and oils and to prevent sharp changes in the quality of fats and oils during the shelf life.
  • Antioxidants commonly used in oils and fats include: tert-butylhydroquinone (TBHQ), dibutylhydroxytoluene (BHT), polyglycerol ricinoleate (PGPR), butylhydroxyanisole (BHA); however, Microbial oils are mainly used in sensitive populations such as infants and pregnant women. These chemically synthesized antioxidants are not suitable for the foods of these two groups of people.
  • antioxidants such as vitamin E.
  • Most of the existing antioxidants added to microbial oils and fats are single antioxidants, and the antioxidant performance is not stable, and cannot provide good antioxidant protection during the shelf life of the product.
  • the object of the present invention is to overcome the problems that the prior art easily leads to oxidation of fats and oils, and easily generates or mixes harmful substances during processing, and provides a method for improving the stability and safety of microbial fats and oils.
  • Oxidation and isomerization of unsaturated microbial oils and fats can improve the stability of oils and fats; reduce harmful substances such as polycyclic aromatic hydrocarbons and 3-chloropropanol in oils and fats, and improve the safety of oils and fats.
  • the present invention provides a method for improving the stability and safety of microbial oils and fats by controlling the peroxide value, anisidine value, acid value, free fatty acid, moisture, and 3-chloropropanol content of the microbial oils and fats.
  • Improve the stability and safety of grease including the following aspects: a) vacuum dehydration of crude oil, vacuum degassing and nitrogen filling, and refrigerated storage; b) the storage, transportation, and processing equipment of grease is made of stainless steel under oxygen-barrier conditions Carry out; c) control the content of oxygen, metal ions and chloride ions in water or steam used in the refining process; d) quickly cool the refined oil to below 35 ° C, and add a combined antioxidant.
  • the storage temperature of the cold wool reservoir is 0-10 ° C, and more preferably 5-8 ° C. It can reduce the peroxide value, anisidine value and acid value of microbial oils.
  • the oil storage, transportation, and processing device includes all reaction kettles, pipes, and valves used for refining; and the stainless steel material is 304L, 316, or 316L stainless steel. It can control the peroxide value, 3-chloropropanol and heavy metal content of microbial oils and fats.
  • the oxygen-blocking condition is vacuuming to isolate oxygen or nitrogen-filling to isolate oxygen. It can reduce the peroxide value, anisidine value and moisture in microbial oils.
  • the water used is secondary reverse osmosis purified water, and the free chlorine content in the water is ⁇ 0.05mg / L.
  • the combined antioxidant is a combination of two or more of vitamin E, vitamin C palmitate, lecithin, and rosemary.
  • the combined antioxidant is: vitamin E1000-1500ppm and vitamin C palmitate 1000-1200ppm, or vitamin E1000-1500ppm, vitamin C palmitate 1000-1200ppm and lecithin 5000ppm or vitamin E1000-1500ppm, vitamins C palmitate 1000-1200 ppm and rosemary 1000-1200 ppm. It can reduce the peroxide value and anisidine value of microbial oils.
  • the product oil produced by using the method for improving the stability and safety of microbial fats and oils has anisidine value of 10 or less, acid value not exceeding 0.8 mg / g in terms of KOH, peroxide value not exceeding 3 meq / kg, and 3 of them
  • the content of chloropropanol is not higher than 200 ⁇ g / kg, the content of trans fatty acids is not higher than 0.8%, and the content of unsaponifiables is not higher than 3.5%.
  • the finished microbial oils have lower peroxide value, anisidine value, acid value, free fatty acid, moisture, and 3-chloropropanol content; the OSI value at 80 ° C is greater than 10 hours, and the polycyclic Aromatic hydrocarbon (PAH) content is less than 1ppb, 3-MCPD content is ⁇ 100 ⁇ g / kg, and the taste is refreshing and non-greasy.
  • PAH Polycyclic Aromatic hydrocarbon
  • the method for improving the stability and safety of microbial oils and fats according to the present invention is used for polyunsaturated microbial oils and fats, and mainly refers to docosahexaenoic acid (DHA) derived from algae oil and fish oil, and docosa tetracarbonate derived from fungi.
  • Enoic acid (ARA) can also be used for other edible vegetable fats, including but not limited to palm oil, rapeseed oil, peanut oil, tea seed oil, soybean oil, olive oil, and sunflower oil.
  • the measures in several aspects cover the entire production, transfer, and storage processes of crude oil storage, refining, and refined oil storage, through crude oil storage, refining, and finished products.
  • the process of oil storage is reflected.
  • the crude oil used is the Mortierella alpine oil and Schizochytrium oil obtained by the inventors during production.
  • Nitrogen produced by the supporting nitrogen generating unit (Guangdong Zhongshan Ji Hi-Tech Co., Ltd., JH-PN49-10) contains 99.99% nitrogen, and the deodorization process uses high-purity nitrogen with a content of 99.999%.
  • Vacuum extraction is performed by a vacuum source system consisting of ZJP1200C, ZJ600B, ZJ300B three-stage Roots vacuum pumps and 2BE1-202 water ring vacuum pumps made by Ma Debao Vacuum Equipment Group Co., Ltd.
  • the system consists of a first-stage water ring pump and a second-stage rotary vane vacuum pump. . All the water used is pure reverse osmosis water. It is produced by the supporting reverse osmosis water production system (Jiangsu Yixing Dexing Environmental Protection Co., Ltd., DX3000). It controls the concentration of metal ions and chloride ions in the water, which is the quality of the subsequent metal ions to the product. The impact of 3-MCPD control creates conditions.
  • the winterization is carried out in a 3m 3 winterization tank, which is kept cold by indirect refrigeration medium cooling;
  • the plate and frame filter press uses XA / GF40 / 800-UK type products of Shandong Jingjin Company, and the filter cloth is made of polypropylene.
  • the deoxidized water vapor is produced by Ningbo Boliweig Environmental Protection Equipment Co., Ltd.'s GMF360-0.8 boiler.
  • Anisidine value and peroxide value, OSI value, PAH (or polycyclic aromatic hydrocarbon) content, trans fatty acid content, and 3-MCPD content were measured using national standard methods, and all reagents used were commercially available ordinary products.
  • the water used for refining is secondary reverse osmosis purified water, and the free chlorine content in the water is ⁇ 0.05mg / L. All reactors, pipes and valves used for refining are made of 304L, 316 or 316L stainless steel.
  • Hair oil treatment The hair oil is dehydrated, vacuum degassed, filled with nitrogen and stored in a 304L stainless steel storage tank under refrigeration at 6 ° C.
  • Pre-washing add secondary reverse osmosis purified water with an oil weight of 10% and citric acid with an oil weight of 3 ⁇ , heat to 85 ° C, and stir at 80 rpm for 20 minutes; separate the water with a two-phase centrifuge.
  • Water-eluting gel add 10% oil of secondary reverse osmosis purified water, heat to 85 ° C, and stir at 80 rpm for 20 minutes; separate the water with a two-phase centrifuge.
  • Acid refining pump the acid refining tank to a negative pressure of -0.1MPa, and transport the crude oil into the acid refining tank by means of negative pressure adsorption; use nitrogen to break the negative pressure to form a slightly positive pressure tank pressure; heat the oil to 75 ° C .; add citric acid (prepared as an aqueous solution with a concentration of 50%) accounting for 4 ⁇ of the oil weight, and stir at 80 rpm for 40 minutes. Then add 10% oil weight of 85 ° C hot water, stir for 20 minutes, and centrifuge to separate the water with a two-phase centrifuge.
  • citric acid prepared as an aqueous solution with a concentration of 50%
  • Water washing three water washings are carried out in the following order: 1 adding reverse osmosis purified water with 10% oil weight, heating to 85 ° C, stirring at 80 rpm for 20 minutes, and separating water with a two-phase centrifuge; 2 adding oil weight 20 % Reverse osmosis purified water, heated to 85 ° C, stirred at 80 rpm for 20 minutes, and separated with a two-phase centrifuge; 3 Add 20% oil by weight reverse osmosis purified water, heated to 85 ° C, and stirred at 80 rpm After 20 minutes, the water was separated in a two-phase centrifuge.
  • Acid refining and water washing add citric acid with an oil weight of 0.2 ⁇ and purified water at 85 ° C with an oil weight of 10%, stir at 80 rpm for 20 minutes, and separate the water with a two-phase centrifuge.
  • the oil is then sent to the low-temperature winterization tank with nitrogen pressure, and the temperature is lowered (see Table 1 for temperature reduction program), and the low-temperature winterization is performed.
  • the low-temperature winterization temperature is -5 ° C, and the time is 90 hours. 0.2MPa.
  • Deodorization The decolorized fat is heated to 175 ° C, and the deoxidized steam which accounts for 7% of the weight of the oil is stripped for 220 minutes under a vacuum environment of 70Pa.
  • the deoxidized steam is an electric heating boiler.
  • the steam formed by the second-stage reverse osmosis pure water heating is transported to the deodorization tank using S316L stainless steel pipes; after breaking the vacuum with 99.999% high-purity nitrogen, the oil is transported to the vacuum nitrogen-filled 304L stainless steel product oil for temporary storage In the jar.
  • Temporary storage of refined oil The refined oil is rapidly cooled to below 35 ° C, and 1200 ppm of vitamin E, 1100 ppm of vitamin C palmitate and 5000 ppm of lecithin are added for antioxidant.
  • the hair oil of Schizochytrium oil as follows.
  • the water used for refining is secondary reverse osmosis purified water, and the free chlorine content in the water is ⁇ 0.05mg / L.
  • All reactors, pipes and valves used for refining are made of 304L, 316 or 316L stainless steel.
  • Pre-wash add reverse osmosis purified water with an oil weight of 10% and citric acid with an oil weight of 3 ⁇ , heat to 85 ° C, stir at 80 rpm for 20 minutes, and separate water after standing for 2 hours.
  • Acid refining pump the acid refining tank to a negative pressure of -0.1MPa, and transport the crude oil into the acid refining tank by means of negative pressure adsorption; use nitrogen to break the negative pressure to form a slightly positive pressure tank pressure; heat the oil to At 60 ° C, citric acid (prepared as an aqueous solution with a concentration of 50%) accounting for 6 ⁇ of the oil weight was added and stirred at a speed of 80 rpm for 40 minutes. Then add 10% oil weight of 85 ° C hot water, stir for 20 minutes, and let it stand for 3 hours to separate water.
  • citric acid prepared as an aqueous solution with a concentration of 50%
  • Water washing The water washing process is performed in three times. The processes are: 1 Add reverse osmosis purified water with 10% oil weight, heat to 85 ° C, and stir at 80 rpm for 20 minutes; let it stand for 2 hours to separate water; 2 add Reverse osmosis purified water with 20% oil weight, heated to 85 ° C, and stirred at 80rpm for 20 minutes; after standing for 2 hours, water was separated manually; 3 Add 20% reverse osmosis purified water with oil weight, heated to 85 ° C, to Stir for 20 minutes at 80 rpm; artificially separate water after standing for 2 hours.
  • Acid refining and water washing add citric acid with an oil weight of 0.2 ⁇ and purified water at 85 ° C. with an oil weight of 10%, stir at 80 rpm for 20 minutes, and separate water after standing for 3 hours.
  • the oil is then sent to the low-temperature winterization tank with nitrogen pressure, and the temperature is lowered (see Table 2 for the temperature reduction program), and the low-temperature winterization is performed.
  • the low-temperature winterization temperature is 0 ° C for 120 hours. MPa.
  • Decolorization The oil after winterization is heated to 75 ° C in a vacuum nitrogen-filled environment, and 1% of the oil weight of silica is added, and the mixture is stirred at 120 rpm for 60 minutes; and the activity of 1% of the weight of oil is added. The white clay and activated carbon that accounted for 1% of the oil weight were stirred at 120 rpm for 60 minutes, and then filtered using a plate and frame.
  • Deodorization Under the negative pressure of 100Pa, heat the decolorized oil to 185 ° C, and pass in the deoxidized steam which accounts for 10% of the oil weight to strip for 240 minutes.
  • the deoxidized steam is heated by the electric boiler.
  • the steam formed by heating with Grade I reverse osmosis pure water is transported to the deodorization tank using S316L stainless steel pipes; after breaking the vacuum with 99.999% high-purity nitrogen, the oil is transported to the temporary nitrogen-filled 304L stainless steel product oil storage tank in.
  • Temporary storage of refined oil The refined oil is rapidly cooled to below 35 ° C, and 1500 ppm of vitamin E, 1200 ppm of vitamin C palmitate and 1200 ppm of rosemary are added to resist oxidation.
  • the crude oil using Mortierella alpine is refined according to the method of Example 1.
  • the difference is that after vacuum dehydration, the crude oil is stored at normal temperature and pressure; no vacuum is used except for the dehydration and deodorization processes, and the entire process is not nitrogen-filled.
  • Pipes and appliances used for processing, transportation, and storage are ordinary steel products; the vacuum degree in the deodorization process is 200 Pa, and the nitrogen purity is 99.99%; the water used in the process is demineralized water, and 1500 ppm of vitamin E is added when the oil is temporarily stored.
  • the refining treatment was carried out using the crude oil of Schizochytrium sp. According to the method of Example 1. The difference is that after vacuum dehydration, the crude oil was stored at normal temperature and pressure; no vacuum was applied except for the dehydration and deodorization processes, and the entire process was not nitrogen-filled; The processing, transportation and storage pipes and appliances are ordinary steel products; the vacuum degree in the deodorization process is 200 Pa, and the nitrogen purity is 99.99%.
  • the water used in the process is demineralized water. 5000 ppm of lecithin is added when the oil is temporarily stored.
  • oils and fats can be used for docosahexaenoic acid (DHA) derived from algae oil and fish oil, aracosatetraenoic acid (ARA) derived from fungi, and other edible plants
  • DHA docosahexaenoic acid
  • ARA aracosatetraenoic acid
  • Oils and fats mainly refer to the refining of palm oil, rapeseed oil, peanut oil, tea seed oil, soybean oil, olive oil, and sunflower oil.

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Abstract

Disclosed is a method for improving the stability and safety of microbial oils and fats, comprising adopting deoxygenation and refrigeration measures in the process of transportation and storage of the microbial oils and fats; adopting an oxygen isolation measure, strictly controlling chlorine ion concentration in oil and water, and controlling metal ion, chlorine ion and oxygen concentrations in stripping steam in the process of refining of the microbial oils and fats; transporting or storing the oils and fats as well as the materials and steam used in refining by means of a pipe or container made of stainless steel; and adding a combination of antioxidants in the microbial oils and fats. The method improves the stability of the microbial oils and fats, controls the anisidine, peroxide and OSI values, reduces the content of polycyclic aromatic hydrocarbons and pesticide residues, and improves the safety of the microbial oils and fats. The microbial oils and fats treated by the method have a good mouthfeel, an improved stability and a reduced content of harmful components, and are especially suitable for making infant formula foods, health foods and healthcare foods.

Description

提高微生物油脂稳定性和安全性的方法Method for improving stability and safety of microbial oils 技术领域Technical field
本发明涉及微生物油脂精炼领域，具体涉及一种提高微生物油脂稳定性和安全性的方法。The invention relates to the field of refining microbial oils and fats, in particular to a method for improving the stability and safety of microbial oils and fats.
背景技术Background technique
微生物油脂中多不饱和脂肪酸含量高，油脂的饱和度低，容易氧化导致了微生物油脂稳定性差。而油脂生产、保存过程中，不饱和油脂与氧接触时，“铁”元素是氧化反应的加速剂，提高氧化速度。同时，油脂脱胶、脱皂、脱色尤其是脱臭过程都是在较高的温度条件下进行，而高温、氧气是油脂氧化的两个重要因素。The content of polyunsaturated fatty acids in microbial oils and fats is high, the saturation of the oils and fats is low, and the stability of the microbial oils and fats is easily caused by oxidation. During the production and storage of fats and oils, when unsaturated fats and fats come in contact with oxygen, the "iron" element is an accelerator for the oxidation reaction, which increases the oxidation rate. At the same time, the degumming, degreasing, decoloring, and especially deodorizing processes of fats and oils are carried out at relatively high temperatures, and high temperature and oxygen are two important factors for oxidation of fats and oils.
水或蒸汽中的氧和氯会加速精炼过程中油脂氧化的速度，增加油脂的酸价和过氧化值，并可增加3氯丙酸的产生。不当的加工、存储器具不仅会导致油脂的氧化，还会导致油脂中塑化剂的含量的增高。Oxygen and chlorine in water or steam will accelerate the oxidation of fats and oils during refining, increase the acid value and peroxide value of fats and oils, and increase the production of 3 chloropropionic acid. Improper processing and storage devices will not only lead to oxidation of the oil, but also increase the content of plasticizer in the oil.
油脂氧化是油脂质量改变的主要原因，为此油脂行业通过添加抗氧化剂的措施来延缓油脂氧化进度、避免油脂在保质期内质量的急剧变化。油脂常规使用的抗氧化剂包括：特丁基对苯二酚(TBHQ)、二丁基羟基甲苯(BHT)、聚甘油蓖麻醇酸酯(PGPR)、丁基羟基茴香醚(BHA)；但是，微生物油脂主要用于婴幼儿与孕产妇等敏感人群，这些化学合成的抗氧化剂并不适应于这两类人群的食品中，所以这两类人群食品的生产商尽量避免使用它们，改为使用更为安全的维生素E等抗氧化剂。现有的微生物油脂中添加的抗氧化剂大多为单一的抗氧化剂，抗氧化性能不稳定，不能在产品保质期内起到良好的抗氧化保护作用。Oxidation of fats and oils is the main reason for the change in the quality of fats and oils. To this end, the oil and fats industry has added antioxidants to delay the oxidation of fats and oils and to prevent sharp changes in the quality of fats and oils during the shelf life. Antioxidants commonly used in oils and fats include: tert-butylhydroquinone (TBHQ), dibutylhydroxytoluene (BHT), polyglycerol ricinoleate (PGPR), butylhydroxyanisole (BHA); however, Microbial oils are mainly used in sensitive populations such as infants and pregnant women. These chemically synthesized antioxidants are not suitable for the foods of these two groups of people. Therefore, food manufacturers of these two groups of people try to avoid using them and use more For safe antioxidants such as vitamin E. Most of the existing antioxidants added to microbial oils and fats are single antioxidants, and the antioxidant performance is not stable, and cannot provide good antioxidant protection during the shelf life of the product.
植物油脂原料和加工助剂本身携带的有害成分，不当加工工艺条件形成的有害成分等，均会随着油脂加工过程迁移到油脂中，如果油料生产过程中没有采取高效的控制，这些有害成分最终将会残留在成品油中并会超出安全限量，对油脂的质量安全造成威胁并危害人体健康。氯丙醇类化合物是公认的食品污染物，具有肾脏毒性、生殖毒性、免疫抑制和潜在致癌性。若油脂生产所用的原料受到污染、生产工艺条件不当、加工设备缺陷或故障，以及原料或产品在运输储存过程中受环境和包装材料污染等原因，都可能导致使用油脂中含有一定量的多环芳烃(PAH)。The harmful ingredients carried by vegetable oil raw materials and processing aids themselves, and the harmful ingredients formed by improper processing conditions will migrate to the oil along with the oil processing process. If the oil production process is not effectively controlled, these harmful ingredients will eventually It will remain in the refined oil and will exceed the safety limit, which will threaten the quality and safety of fats and endanger human health. Chloropropanols are recognized as food contaminants with renal toxicity, reproductive toxicity, immunosuppression and potential carcinogenicity. If the raw materials used in the production of oil are contaminated, improper production process conditions, processing equipment is defective or faulty, and the raw materials or products are contaminated by the environment and packaging materials during transportation and storage, all these factors may cause the use of oils and oils to contain a certain amount of polycyclics. Aromatics (PAH).
发明内容Summary of the invention
本发明的目的是为了克服现有技术容易导致油脂氧化，在加工过程中容易产生或者混入有害物质的问题，提供一种提高微生物油脂稳定性和安全性的方法，该方法具有能够较好的防止不饱和微生物油脂的氧化、同分异构化，提高油脂的稳定性；降低油脂中的多环芳烃、3氯丙醇等有害物质，提高油脂的安全性。The object of the present invention is to overcome the problems that the prior art easily leads to oxidation of fats and oils, and easily generates or mixes harmful substances during processing, and provides a method for improving the stability and safety of microbial fats and oils. Oxidation and isomerization of unsaturated microbial oils and fats can improve the stability of oils and fats; reduce harmful substances such as polycyclic aromatic hydrocarbons and 3-chloropropanol in oils and fats, and improve the safety of oils and fats.
为了实现上述目的，本发明提供一种提高微生物油脂稳定性和安全性的方法，通过控制微生物油脂的过氧化值、茴香胺值、酸价、游离脂肪酸、水分、3-氯丙醇含量，来提高油脂的稳定性和安全性，包括以下方面：a)对毛油进行真空脱水，真空脱气充氮，冷藏贮存；b)油脂的存储、运输、加工装置采用不锈钢材质，在隔氧条件下进行；c)控制精炼过程中所用水或蒸汽中氧、金属离子和氯离子的含量；d)将成品油快速降温到35℃以下，并加入组合抗氧化剂。In order to achieve the above object, the present invention provides a method for improving the stability and safety of microbial oils and fats by controlling the peroxide value, anisidine value, acid value, free fatty acid, moisture, and 3-chloropropanol content of the microbial oils and fats. Improve the stability and safety of grease, including the following aspects: a) vacuum dehydration of crude oil, vacuum degassing and nitrogen filling, and refrigerated storage; b) the storage, transportation, and processing equipment of grease is made of stainless steel under oxygen-barrier conditions Carry out; c) control the content of oxygen, metal ions and chloride ions in water or steam used in the refining process; d) quickly cool the refined oil to below 35 ° C, and add a combined antioxidant.
优选地，在a)方面，所述冷毛油藏贮存的温度为0-10℃，进一步优选为5-8℃。可降低微生物油脂的过氧化值、茴香胺值、酸价等。Preferably, in aspect a), the storage temperature of the cold wool reservoir is 0-10 ° C, and more preferably 5-8 ° C. It can reduce the peroxide value, anisidine value and acid value of microbial oils.
优选地，在b)方面，所述油脂的存储、运输、加工装置，包括所有用 于精炼的反应釜、管道与阀门；所述不锈钢材质为304L、316或316L不锈钢材。可控制微生物油脂的过氧化值、3-氯丙醇、重金属含量等。Preferably, in aspect b), the oil storage, transportation, and processing device includes all reaction kettles, pipes, and valves used for refining; and the stainless steel material is 304L, 316, or 316L stainless steel. It can control the peroxide value, 3-chloropropanol and heavy metal content of microbial oils and fats.
优选地，在b)方面，所述隔氧条件为抽真空隔绝氧氧气或者充氮隔绝氧气。可降低微生物油脂中的过氧化值、茴香胺值、水分等。Preferably, in aspect b), the oxygen-blocking condition is vacuuming to isolate oxygen or nitrogen-filling to isolate oxygen. It can reduce the peroxide value, anisidine value and moisture in microbial oils.
优选地，在c)方面，所述控制精炼过程中所用水或蒸汽中氧、金属离子和氯离子的含量的方法中，所用水都是二级反渗透纯净水，水中游离氯含量≤0.05mg/L。Preferably, in the aspect c), in the method for controlling the content of oxygen, metal ions and chloride ions in water or steam used in the refining process, the water used is secondary reverse osmosis purified water, and the free chlorine content in the water is ≤0.05mg / L.
优选地，在c)方面，所述控制精炼过程中所用水或蒸汽中氧、金属离子和氯离子的含量的方法中，汽提所用的蒸汽为经过脱氧处理的二级反渗透纯净水加热所得的蒸汽，具体为，依靠工厂的普通锅炉产生的蒸汽作为热源，或者在脱臭罐附件配套专门的电加热锅炉，将经过脱氧处理的二级反渗透纯净水予以加热形成脱臭专用的汽提蒸汽。输送蒸汽的管道采用S316L或S316材质的不锈钢管道。可降低微生物油脂中的酸价、游离脂肪酸、重金属含量、3-氯丙醇等。Preferably, in aspect c), in the method for controlling the content of oxygen, metal ions and chloride ions in water or steam used in the refining process, the steam used for the stripping is obtained by heating the deoxidized secondary reverse osmosis purified water The steam is specifically based on the steam generated by the ordinary boiler in the factory as a heat source, or a special electric heating boiler attached to the deodorization tank accessory, and the deoxidized secondary reverse osmosis pure water is heated to form the deodorization stripping steam. The pipeline for steam transmission is S316L or S316 stainless steel. Can reduce the acid value, free fatty acids, heavy metal content, 3-chloropropanol, etc. in microbial oils and fats.
优选地，在d)方面，所述组合抗氧化剂为，维生素E、维生素C棕榈酸酯、卵磷脂和迷迭香中两种以上的组合物。Preferably, in aspect d), the combined antioxidant is a combination of two or more of vitamin E, vitamin C palmitate, lecithin, and rosemary.
进一步优选地，所述组合抗氧化剂为，维生素E1000-1500ppm和维生素C棕榈酸酯1000-1200ppm，或者维生素E1000-1500ppm、维生素C棕榈酸酯1000-1200ppm和卵磷脂5000ppm或者维生素E1000-1500ppm、维生素C棕榈酸酯1000-1200ppm和迷迭香1000-1200ppm。可降低微生物油脂的过氧化值、茴香胺值等。Further preferably, the combined antioxidant is: vitamin E1000-1500ppm and vitamin C palmitate 1000-1200ppm, or vitamin E1000-1500ppm, vitamin C palmitate 1000-1200ppm and lecithin 5000ppm or vitamin E1000-1500ppm, vitamins C palmitate 1000-1200 ppm and rosemary 1000-1200 ppm. It can reduce the peroxide value and anisidine value of microbial oils.
使用本发明的提高微生物油脂稳定性和安全性的方法生产的成品油，茴香胺值在10以下、酸价以KOH计不超过0.8mg/g、过氧化值不超过3meq/kg且其中的3氯丙醇含量不高于200μg/kg，反式脂肪酸含量不高于0.8％，不皂化物含量不高于3.5％。The product oil produced by using the method for improving the stability and safety of microbial fats and oils has anisidine value of 10 or less, acid value not exceeding 0.8 mg / g in terms of KOH, peroxide value not exceeding 3 meq / kg, and 3 of them The content of chloropropanol is not higher than 200 μg / kg, the content of trans fatty acids is not higher than 0.8%, and the content of unsaponifiables is not higher than 3.5%.
通过上述技术方案，得到的成品微生物油脂，过氧化值、茴香胺值、酸价、游离脂肪酸、水分、3-氯丙醇含量均较低；在80℃时的OSI值大于10小时，多环芳烃(PAH)含量小于1ppb，3-MCPD含量≤100μg/kg，且口感清爽、无油腻感。Through the above technical scheme, the finished microbial oils have lower peroxide value, anisidine value, acid value, free fatty acid, moisture, and 3-chloropropanol content; the OSI value at 80 ° C is greater than 10 hours, and the polycyclic Aromatic hydrocarbon (PAH) content is less than 1ppb, 3-MCPD content is ≤100μg / kg, and the taste is refreshing and non-greasy.
本发明的提高微生物油脂稳定性和安全性的方法，用于多不饱和微生物油脂，主要是指藻油来源和鱼油来源的二十二碳六烯酸(DHA)、真菌来源的二十碳四烯酸(ARA)。也可用于其他食用植物油脂，包括但不限于棕榈油、菜籽油、花生油、茶籽油、大豆油、橄榄油、葵花籽油。The method for improving the stability and safety of microbial oils and fats according to the present invention is used for polyunsaturated microbial oils and fats, and mainly refers to docosahexaenoic acid (DHA) derived from algae oil and fish oil, and docosa tetracarbonate derived from fungi. Enoic acid (ARA). It can also be used for other edible vegetable fats, including but not limited to palm oil, rapeseed oil, peanut oil, tea seed oil, soybean oil, olive oil, and sunflower oil.
具体实施方式detailed description
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Hereinafter, specific embodiments of the present invention will be described in detail. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not intended to limit the present invention.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the end values of each range, between the end values of each range and individual point values, and between the individual point values, one or more new numerical ranges can be obtained by combining each other. These values The scope should be considered to be specifically disclosed herein.
在本发明的提高微生物油脂稳定性和安全性的方法中，几个方面的措施覆盖于毛油储存、精炼和成品油储存的整个生产、转运和贮存过程中，通过毛油储存、精炼和成品油储存的工艺得到体现。In the method for improving the stability and safety of microbial oils and fats of the present invention, the measures in several aspects cover the entire production, transfer, and storage processes of crude oil storage, refining, and refined oil storage, through crude oil storage, refining, and finished products. The process of oil storage is reflected.
以下将通过实施例对本发明进行详细描述。以下实施例中，所用毛油为发明人在生产中取得的高山被孢霉油脂与裂壶藻油脂。氮气由配套制氮机组(广东中山积高科技有限公司，JH-PN49-10)产生的含量为99.99％氮气，脱臭工序所用的为含量为99.999％的高纯氮气。抽真空由马德保真空设备集团有限公司的ZJP1200C、ZJ600B、ZJ300B三级罗茨真空泵和2BE1-202水 环真空泵组成的真空源***进行，该***由一级水环泵，加二级旋片真空泵组成。所有使用的水均为反渗透的纯净水，由配套的反渗透制水***(江苏宜兴德兴环保有限公司，DX3000)制得，控制水中金属离子、氯离子浓度，为后续金属离子对产品质量的影响、3-MCPD的控制创造条件。冬化在3m 3冬化罐进行，通过间接制冷介质降温保持低温；板框压滤机使用山东景津公司的XA/GF40/800-UK型的产品，滤布使用聚丙烯材质滤布，压力由板框压滤机设定；脱水在脱水罐中进行，可设定温度、压力；叶滤机使用江苏巨能机械设备有限公司的NYB-7产品。脱氧水蒸汽由宁波波力维格环保设备有限公司的GMF360-0.8锅炉产生。茴香胺值与过氧化值、OSI值、PAH(或多环芳烃)含量、反式脂肪酸含量、3-MCPD含量采用国家标准方法测得，所用试剂均为市售普通产品。 Hereinafter, the present invention will be described in detail through examples. In the following examples, the crude oil used is the Mortierella alpine oil and Schizochytrium oil obtained by the inventors during production. Nitrogen produced by the supporting nitrogen generating unit (Guangdong Zhongshan Ji Hi-Tech Co., Ltd., JH-PN49-10) contains 99.99% nitrogen, and the deodorization process uses high-purity nitrogen with a content of 99.999%. Vacuum extraction is performed by a vacuum source system consisting of ZJP1200C, ZJ600B, ZJ300B three-stage Roots vacuum pumps and 2BE1-202 water ring vacuum pumps made by Ma Debao Vacuum Equipment Group Co., Ltd. The system consists of a first-stage water ring pump and a second-stage rotary vane vacuum pump. . All the water used is pure reverse osmosis water. It is produced by the supporting reverse osmosis water production system (Jiangsu Yixing Dexing Environmental Protection Co., Ltd., DX3000). It controls the concentration of metal ions and chloride ions in the water, which is the quality of the subsequent metal ions to the product. The impact of 3-MCPD control creates conditions. The winterization is carried out in a 3m 3 winterization tank, which is kept cold by indirect refrigeration medium cooling; the plate and frame filter press uses XA / GF40 / 800-UK type products of Shandong Jingjin Company, and the filter cloth is made of polypropylene. Set by plate and frame filter press; dewatering is carried out in the dewatering tank, and the temperature and pressure can be set; leaf filter uses NYB-7 products of Jiangsu Juneng Machinery Equipment Co., Ltd. The deoxidized water vapor is produced by Ningbo Boliweig Environmental Protection Equipment Co., Ltd.'s GMF360-0.8 boiler. Anisidine value and peroxide value, OSI value, PAH (or polycyclic aromatic hydrocarbon) content, trans fatty acid content, and 3-MCPD content were measured using national standard methods, and all reagents used were commercially available ordinary products.
实施例1Example 1
使用高山被孢霉油脂的毛油，按下述步骤处理。精炼所用的水都是二级反渗透纯净水，水中游离氯含量≤0.05mg/L。所有用于精炼的反应釜、管道与阀门均由304L、316或316L不锈钢材材料制成。Use the hair oil of Mortierella alpine to process the following steps. The water used for refining is secondary reverse osmosis purified water, and the free chlorine content in the water is ≤0.05mg / L. All reactors, pipes and valves used for refining are made of 304L, 316 or 316L stainless steel.
1)毛油处理：毛油经脱水、真空脱气，充入氮气在6℃条件下冷藏保存于304L不锈钢材质的储存罐中。1) Hair oil treatment: The hair oil is dehydrated, vacuum degassed, filled with nitrogen and stored in a 304L stainless steel storage tank under refrigeration at 6 ° C.
2)预水洗：加入油重10％的二级反渗透纯净水、油重3‰的柠檬酸，加热到85℃，以80rpm的转速搅拌20分钟；用二相离心机分水。2) Pre-washing: add secondary reverse osmosis purified water with an oil weight of 10% and citric acid with an oil weight of 3 ‰, heat to 85 ° C, and stir at 80 rpm for 20 minutes; separate the water with a two-phase centrifuge.
3)水洗脱胶：加入油重10％的二级反渗透纯净水，加热到85℃，以80rpm的转速搅拌20分钟；用二相离心机分水。3) Water-eluting gel: add 10% oil of secondary reverse osmosis purified water, heat to 85 ° C, and stir at 80 rpm for 20 minutes; separate the water with a two-phase centrifuge.
4)酸炼：将酸炼罐抽负压到-0.1MPa,用负压吸附的方式将毛油输送到酸炼罐中；用氮气破负压形成微正压的罐压；将油加热到75℃；加入占油重4‰的柠檬酸(配制成浓度为50％的水溶液加入)，以80rpm的转速搅拌40分钟。再加入油重10％的85℃热水，搅拌20分钟，用二相离心机离心分水。4) Acid refining: pump the acid refining tank to a negative pressure of -0.1MPa, and transport the crude oil into the acid refining tank by means of negative pressure adsorption; use nitrogen to break the negative pressure to form a slightly positive pressure tank pressure; heat the oil to 75 ° C .; add citric acid (prepared as an aqueous solution with a concentration of 50%) accounting for 4 ‰ of the oil weight, and stir at 80 rpm for 40 minutes. Then add 10% oil weight of 85 ° C hot water, stir for 20 minutes, and centrifuge to separate the water with a two-phase centrifuge.
5)碱炼水洗：先将碱炼罐抽负压，将酸炼罐中油脂用氮气压送到碱炼罐中。将油加热到45℃，根据油脂酸价计算加碱量(加碱量＝7.13×10 -4×酸价×油重)，加入40％的氢氧化钠溶液，以80rpm的转速搅拌50分钟；将油脂温度升温到80℃，再加入油重5％的85℃纯净水，以80rpm的速度搅拌15分钟，离心用二相离心机去除皂角。 5) Washing with alkali refining: first pump the alkali refining tank to a negative pressure, and pressurize the oil in the acid refining tank with nitrogen to the alkali refining tank. Heat the oil to 45 ° C, calculate the amount of alkali added based on the acid value of the fat (addition amount = 7.13 × 10 -4 × acid value × oil weight), add 40% sodium hydroxide solution, and stir at 80 rpm for 50 minutes; The temperature of the oil and fat was increased to 80 ° C, and then 85% of purified water with an oil weight of 5% was added, and the mixture was stirred at 80 rpm for 15 minutes, and the saponin was removed by centrifugation with a two-phase centrifuge.
6)水洗：进行三次水洗，工艺依次为：①加入油重10％的反渗透纯净水，加热到85℃，以80rpm的转速搅拌20分钟，用二相离心机分水；②加入油重20％的反渗透纯净水，加热到85℃，以80rpm的转速搅拌20分钟，用二相离心机分水；③加入油重20％的反渗透纯净水，加热到85℃，以80rpm的转速搅拌20分钟，用二相离心机分水。6) Water washing: three water washings are carried out in the following order: ① adding reverse osmosis purified water with 10% oil weight, heating to 85 ° C, stirring at 80 rpm for 20 minutes, and separating water with a two-phase centrifuge; ② adding oil weight 20 % Reverse osmosis purified water, heated to 85 ° C, stirred at 80 rpm for 20 minutes, and separated with a two-phase centrifuge; ③ Add 20% oil by weight reverse osmosis purified water, heated to 85 ° C, and stirred at 80 rpm After 20 minutes, the water was separated in a two-phase centrifuge.
7)酸炼水洗：加入油重量0.2‰的柠檬酸、油重10％的85℃纯净水，以80rpm的转速搅拌20分钟，用二相离心机分水。7) Acid refining and water washing: add citric acid with an oil weight of 0.2 ‰ and purified water at 85 ° C with an oil weight of 10%, stir at 80 rpm for 20 minutes, and separate the water with a two-phase centrifuge.
8)冬化：先将脱水罐抽负压，将碱炼油用氮气压送到脱水罐中，再油脂升温到85℃，继续抽负压到-0.1MPa，脱水40分钟。将脱水油压入抽负压的常温冬化罐中，常温冬化温度25℃、时间20小时，板过滤框过滤，过滤压力0.1MPa。将油脂压送到脱水罐中再次脱水，脱水条件同第一次脱水。再将油脂用氮气压送到低温冬化罐中，程序降温度(降温程序见表1)，进行低温冬化处理，低温冬化温度-5℃，时间90小时，用板框过滤，过滤压力0.2MPa。8) Winterization: first pump the dehydration tank to a negative pressure, press the alkali refinery with nitrogen to the dehydration tank, and then heat the oil to 85 ° C, continue to pump negative pressure to -0.1MPa, and dehydrate for 40 minutes. The dehydrated oil is pressed into a normal-temperature winterization tank under negative pressure, and the normal-temperature winterization temperature is 25 ° C. for a period of 20 hours. The plate filter frame is used for filtration, and the filtration pressure is 0.1 MPa. The fat is pressed into the dehydration tank for dehydration again, and the dehydration conditions are the same as the first dehydration. The oil is then sent to the low-temperature winterization tank with nitrogen pressure, and the temperature is lowered (see Table 1 for temperature reduction program), and the low-temperature winterization is performed. The low-temperature winterization temperature is -5 ° C, and the time is 90 hours. 0.2MPa.
表1Table 1
程序编号Program number 11 22 33 44 55 66 77 88 99 1010 1111 1212 1313
温度(℃)Temperature (℃) 7575 6565 5555 4545 4242 3939 3636 3232 2828 2525 21twenty one 1919 1717
时间(分)Time (minutes) 3030 3030 3030 6060 6060 6060 6060 9090 9090 9090 120120 9090 9090
程序编号Program number 1414 1515 1616 1717 1818 1919 2020 21twenty one 22twenty two 23twenty three 24twenty four 2525 2626
温度(℃)Temperature (℃) 1616 1515 1414 1313 1212 12.212.2 12.412.4 12.712.7 13.113.1 13.513.5 1414 1212 1010
时间(分)Time (minutes) 6060 6060 6060 6060 6060 6060 6060 6060 6060 6060 6060 6060 6060
程序编号Program number 2727 2828 2929 3030 3131 3232 3333 3434 3535 3636 3737 3838 3939
温度(℃)Temperature (℃) 88 66 44 22 00 -2-2 -4-4 -5-5 -5-5 -5-5 -5-5 -5-5 -5-5
时间(分)Time (minutes) 6060 6060 6060 6060 6060 6060 6060 3030 600600 600600 900900 900900 270270
9)脱色：经冬化后的油脂在真空充氮的环境下加热到70℃，加入占油重1.5％的二氧化硅，以120rpm的速度搅拌60分钟；再加入占油重2％的活性白土和占油重2％的活性碳，以120rpm的速度搅拌60分钟，用叶滤机过滤。9) Decolorization: The fat after winterization is heated to 70 ° C under a vacuum nitrogen-filled environment, and 1.5% of the oil weight of silica is added, and the mixture is stirred at 120 rpm for 60 minutes; and the activity of 2% of the oil weight is added. The white clay and activated carbon, which accounted for 2% by weight of the oil, were stirred at 120 rpm for 60 minutes and filtered with a leaf filter.
10)脱臭：将经脱色的油脂加热到175℃，在70Pa真空环境下，通入占油重量7％的脱氧蒸汽汽提220分钟，所述脱氧蒸汽为用电加热锅炉，将经过脱氧处理的二级反渗透纯净水予以加热形成的蒸汽，采用S316L材质的不锈钢管道输送到脱臭罐中；用99.999％高纯氮破真空后，将油脂输送到真空充氮的304L不锈钢材质的成品油暂存罐中。10) Deodorization: The decolorized fat is heated to 175 ° C, and the deoxidized steam which accounts for 7% of the weight of the oil is stripped for 220 minutes under a vacuum environment of 70Pa. The deoxidized steam is an electric heating boiler. The steam formed by the second-stage reverse osmosis pure water heating is transported to the deodorization tank using S316L stainless steel pipes; after breaking the vacuum with 99.999% high-purity nitrogen, the oil is transported to the vacuum nitrogen-filled 304L stainless steel product oil for temporary storage In the jar.
11)成品油暂存：将成品油迅速降温到35℃以下，加入1200ppm的维生素E、1100ppm的维生素C棕榈酸酯和5000ppm的卵磷脂抗氧化。11) Temporary storage of refined oil: The refined oil is rapidly cooled to below 35 ° C, and 1200 ppm of vitamin E, 1100 ppm of vitamin C palmitate and 5000 ppm of lecithin are added for antioxidant.
实施例2Example 2
使用裂壶藻油脂的毛油，按下述步骤处理。精炼所用的水都是二级反渗透纯净水，水中游离氯含量≤0.05mg/L。所有用于精炼的反应釜、管道与阀门均由304L、316或316L不锈钢材材料制成。Use the hair oil of Schizochytrium oil as follows. The water used for refining is secondary reverse osmosis purified water, and the free chlorine content in the water is ≤0.05mg / L. All reactors, pipes and valves used for refining are made of 304L, 316 or 316L stainless steel.
1)毛油处理：毛油经脱水、真空脱气，充入氮气在8℃条件下冷藏保存于304L不锈钢材质的储存罐中。1) Treatment of crude oil: The crude oil is dehydrated, vacuum degassed, filled with nitrogen and stored in a 304L stainless steel storage tank under refrigeration at 8 ° C.
2)预水洗：加入油重10％的反渗透纯净水、油重3‰的柠檬酸，加热到85℃，以80rpm的转速搅拌20分钟，静置2小时后人工分水。2) Pre-wash: add reverse osmosis purified water with an oil weight of 10% and citric acid with an oil weight of 3 ‰, heat to 85 ° C, stir at 80 rpm for 20 minutes, and separate water after standing for 2 hours.
3)水洗脱胶：加入油重10％的反渗透纯净水，加热到85℃，以80rpm的转速搅拌20分钟，静置2小时后人工分水。3) Water-eluting gel: Add reverse osmosis purified water with 10% oil weight, heat to 85 ° C, stir at 80 rpm for 20 minutes, and let it separate for 2 hours.
4)酸炼：将酸炼罐抽负压到-0.1MPa,用负压吸附的方式将毛油输送到 酸炼罐中；用氮气破负压形成微正压的罐压；将油加热到60℃，加入占油重6‰的柠檬酸(配制成浓度为50％的水溶液)，以80rpm的转速搅拌40分钟。再加入油重10％的85℃热水，搅拌20分钟，静置3小时后人工分水。4) Acid refining: pump the acid refining tank to a negative pressure of -0.1MPa, and transport the crude oil into the acid refining tank by means of negative pressure adsorption; use nitrogen to break the negative pressure to form a slightly positive pressure tank pressure; heat the oil to At 60 ° C, citric acid (prepared as an aqueous solution with a concentration of 50%) accounting for 6 ‰ of the oil weight was added and stirred at a speed of 80 rpm for 40 minutes. Then add 10% oil weight of 85 ° C hot water, stir for 20 minutes, and let it stand for 3 hours to separate water.
5)碱炼水洗：先将碱炼罐抽负压，将酸炼罐中油脂用氮气压送到碱炼罐中。将油加热到70℃，根据油脂酸价计算加碱量(加碱量＝7.13×10 -4×酸价×油重)，加入40％的氢氧化钠溶液，以80rpm的转速搅拌60分钟；将油脂温度升温到80℃，再加入油重5％的85℃纯净水，以80rpm的速度搅拌20分钟；静置3小时后采用微孔过滤器将皂角过滤去除。 5) Washing with alkali refining: first pump the alkali refining tank to a negative pressure, and pressurize the oil in the acid refining tank with nitrogen to the alkali refining tank. Heat the oil to 70 ° C, calculate the amount of alkali added based on the acid value of the fat (addition amount = 7.13 × 10 -4 × acid value × oil weight), add 40% sodium hydroxide solution, and stir at 80 rpm for 60 minutes; The temperature of the oil and fat was increased to 80 ° C., and then purified water with 5% oil weight and 85 ° C. was added and stirred at 80 rpm for 20 minutes. After standing for 3 hours, the soap angle was removed by using a microporous filter.
6)水洗：水洗工序分三次进行，工艺分别为：①加入油重10％的反渗透纯净水，加热到85℃，以80rpm的转速搅拌20分钟；静置2小时后人工分水；②加入油重20％的反渗透纯净水，加热到85℃，以80rpm的转速搅拌20分钟；静置2小时后人工分水；③加入油重20％的反渗透纯净水，加热到85℃，以80rpm的转速搅拌20分钟；静置2小时后人工分水。6) Water washing: The water washing process is performed in three times. The processes are: ① Add reverse osmosis purified water with 10% oil weight, heat to 85 ° C, and stir at 80 rpm for 20 minutes; let it stand for 2 hours to separate water; ② add Reverse osmosis purified water with 20% oil weight, heated to 85 ° C, and stirred at 80rpm for 20 minutes; after standing for 2 hours, water was separated manually; ③ Add 20% reverse osmosis purified water with oil weight, heated to 85 ° C, to Stir for 20 minutes at 80 rpm; artificially separate water after standing for 2 hours.
7)酸炼水洗：加入油重量0.2‰的柠檬酸、油重10％的85℃纯净水，以80rpm的转速搅拌20分钟，静置3小时后人工分水。7) Acid refining and water washing: add citric acid with an oil weight of 0.2 ‰ and purified water at 85 ° C. with an oil weight of 10%, stir at 80 rpm for 20 minutes, and separate water after standing for 3 hours.
8)冬化：先将脱水罐抽负压，将碱炼油用氮气压送到脱水罐中，再油脂升温到90℃，继续抽负压到-0.1MPa，脱水40分钟。将脱水油压入抽负压的常温冬化罐中，常温冬化温度35℃、时间40小时，板过滤框过滤，过滤压力0.1MPa。将油脂压送到脱水罐中再次脱水，脱水条件同第一次脱水。再将油脂用氮气压送到低温冬化罐中，程序降温度(降温程序见表2)，进行低温冬化处理，低温冬化温度0℃，时间120小时，用板框过滤，过滤压力0.2MPa。8) Winterization: first pump the dehydration tank to a negative pressure, press the alkali refinery with nitrogen to the dehydration tank, and then heat the oil to 90 ° C, continue to pump negative pressure to -0.1MPa, and dehydrate for 40 minutes. The dehydrated oil is pressed into a normal-temperature winterization tank under negative pressure. The normal-temperature winterization temperature is 35 ° C. and the time is 40 hours. The plate filter frame is used for filtration, and the filtration pressure is 0.1 MPa. The fat is pressed into the dehydration tank for dehydration again, and the dehydration conditions are the same as the first dehydration. The oil is then sent to the low-temperature winterization tank with nitrogen pressure, and the temperature is lowered (see Table 2 for the temperature reduction program), and the low-temperature winterization is performed. The low-temperature winterization temperature is 0 ° C for 120 hours. MPa.
表2Table 2
程序编号Program number 11 22 33 44 55 66 77 88 99 1010 1111 1212 1313
温度(℃)Temperature (℃) 7575 6565 5555 4545 4242 3939 3636 3232 2828 2525 21twenty one 1919 1717
时间(分)Time (minutes) 3030 3030 3030 6060 6060 6060 6060 9090 9090 9090 120120 9090 9090
程序编号Program number 1414 1515 1616 1717 1818 1919 2020 21twenty one 22twenty two 23twenty three 24twenty four 2525 2626
温度(℃)Temperature (℃) 1616 1515 1414 1313 1212 12.212.2 12.412.4 12.712.7 13.113.1 13.513.5 1414 1212 1010
时间(分)Time (minutes) 6060 6060 6060 6060 6060 6060 6060 6060 6060 6060 6060 6060 6060
程序编号Program number 2727 2828 2929 3030 3131 3232 3333 3434 3535 3636 3737 3838  Zh
温度(℃)Temperature (℃) 88 66 44 22 00 00 00 00 00 00 00 00  Zh
时间(分)Time (minutes) 6060 6060 6060 6060 6060 600600 600600 900900 900900 900900 900900 420420  Zh
9)脱色：经冬化后的油脂在真空充氮的环境下加热到75℃，加入占油重1％的二氧化硅，以120rpm的转速搅拌60分钟；再加入占油重1％的活性白土、和占油重1％的活性碳，以120rpm的转速搅拌60分钟后采用板框过滤。9) Decolorization: The oil after winterization is heated to 75 ° C in a vacuum nitrogen-filled environment, and 1% of the oil weight of silica is added, and the mixture is stirred at 120 rpm for 60 minutes; and the activity of 1% of the weight of oil is added. The white clay and activated carbon that accounted for 1% of the oil weight were stirred at 120 rpm for 60 minutes, and then filtered using a plate and frame.
10)脱臭：在100Pa的负压条件下，将经脱色的油脂加热到185℃，通入占油重量10％的脱氧蒸汽汽提240分钟，脱氧蒸汽用电加热锅炉，将经过脱氧处理的二级反渗透纯净水予以加热形成的蒸汽，采用S316L材质的不锈钢管道输送到脱臭罐中；用99.999％高纯氮破真空后，将油脂输送到真空充氮的304L不锈钢材质的成品油暂存罐中。10) Deodorization: Under the negative pressure of 100Pa, heat the decolorized oil to 185 ° C, and pass in the deoxidized steam which accounts for 10% of the oil weight to strip for 240 minutes. The deoxidized steam is heated by the electric boiler. The steam formed by heating with Grade I reverse osmosis pure water is transported to the deodorization tank using S316L stainless steel pipes; after breaking the vacuum with 99.999% high-purity nitrogen, the oil is transported to the temporary nitrogen-filled 304L stainless steel product oil storage tank in.
11)成品油暂存：将成品油迅速降温到35℃以下，加入1500ppm的维生素E、1200ppm的维生素C棕榈酸酯和1200ppm的迷迭香抗氧化。11) Temporary storage of refined oil: The refined oil is rapidly cooled to below 35 ° C, and 1500 ppm of vitamin E, 1200 ppm of vitamin C palmitate and 1200 ppm of rosemary are added to resist oxidation.
对比例1Comparative Example 1
使用高山被孢霉油脂的毛油按照实施例1的方法进行精炼处理，不同的是，毛油经真空脱水后，常温常压贮存；除脱水、脱臭工艺外不抽真空，整个过程不充氮；加工、输送、储存用管道、器具为普通钢铁制产品；脱臭工艺中真空度为200Pa、破真空氮气纯度99.99％，工艺中所用水为软化水，成品油暂存时加入1500ppm的维生素E。The crude oil using Mortierella alpine is refined according to the method of Example 1. The difference is that after vacuum dehydration, the crude oil is stored at normal temperature and pressure; no vacuum is used except for the dehydration and deodorization processes, and the entire process is not nitrogen-filled. Pipes and appliances used for processing, transportation, and storage are ordinary steel products; the vacuum degree in the deodorization process is 200 Pa, and the nitrogen purity is 99.99%; the water used in the process is demineralized water, and 1500 ppm of vitamin E is added when the oil is temporarily stored.
对比例2Comparative Example 2
使用裂壶藻油脂的毛油按照实施例1的方法进行精炼处理，不同的是，毛油经真空脱水后，常温常压贮存；除脱水、脱臭工艺外不抽真空，整个过 程不充氮；加工、输送、储存用管道、器具为普通钢铁制产品；脱臭工艺中真空度200Pa、破真空氮气纯度99.99％，工艺中所用水为软化水，成品油暂存时加入5000ppm的卵磷脂。The refining treatment was carried out using the crude oil of Schizochytrium sp. According to the method of Example 1. The difference is that after vacuum dehydration, the crude oil was stored at normal temperature and pressure; no vacuum was applied except for the dehydration and deodorization processes, and the entire process was not nitrogen-filled; The processing, transportation and storage pipes and appliances are ordinary steel products; the vacuum degree in the deodorization process is 200 Pa, and the nitrogen purity is 99.99%. The water used in the process is demineralized water. 5000 ppm of lecithin is added when the oil is temporarily stored.
对使用上述方法精炼的成品油脂检测茴香胺值、酸价、过氧化值、OSI值、多环芳烃含量、3-MCPD含量等，检测结果如表3所示。The refined oils and fats refined by the above method were tested for anisidine value, acid value, peroxide value, OSI value, polycyclic aromatic hydrocarbon content, 3-MCPD content, etc. The test results are shown in Table 3.
表3table 3
 Zh 实施例1Example 1 实施例2Example 2 对比例1Comparative Example 1 对比例2Comparative Example 2
水分(％)Moisture (%) 0.020.02 0.0240.024 0.0320.032 0.0280.028
酸价(mg/g)Acid value (mg / g) 0.180.18 0.140.14 1.431.43 1.511.51
过氧化值(meq/kg)Peroxide value (meq / kg) 0.080.08 0.120.12 3.03.0 4.44.4
茴香胺值Anisidine value 2.32.3 2.92.9 1111 1313
游离脂肪酸(％)Free fatty acid (%) 无no 无no 0.320.32 0.280.28
3-MCPD(μg/kg)3-MCPD (μg / kg) 7676 8282 325325 412412
PAH(ppb)PAH (ppb) 0.810.81 0.750.75 1.351.35 1.781.78
OSI值(80℃)(h)OSI value (80 ℃) (h) 16.216.2 15.915.9 5.85.8 6.36.3
通过表3的结果可以看出，采用本发明提高微生物油脂稳定性和安全性的方法的实施例，抗氧化性更强，有害成分含量更低，具有明显更好的稳定性和安全性。From the results in Table 3, it can be seen that the embodiment of the method for improving the stability and safety of microbial oils according to the present invention has stronger oxidation resistance, lower content of harmful ingredients, and has significantly better stability and safety.
本发明的提高微生物油脂稳定性和安全性的方法，可用于藻油来源和鱼油来源的二十二碳六烯酸(DHA)、真菌来源的二十碳四烯酸(ARA)和其他食用植物油脂，主要是指棕榈油、菜籽油、花生油、茶籽油、大豆油、橄榄油、葵花籽油等的精炼。The method for improving the stability and safety of microbial oils and fats can be used for docosahexaenoic acid (DHA) derived from algae oil and fish oil, aracosatetraenoic acid (ARA) derived from fungi, and other edible plants Oils and fats mainly refer to the refining of palm oil, rapeseed oil, peanut oil, tea seed oil, soybean oil, olive oil, and sunflower oil.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包 括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be regarded as the disclosure of the present invention. All belong to the protection scope of the present invention.

Claims (10)

  1. 一种提高微生物油脂稳定性和安全性的方法，通过控制微生物油脂的过氧化值、茴香胺值、酸价、游离脂肪酸、水分、3-氯丙醇含量，来提高油脂的稳定性和安全性，其特征在于，包括以下方面：a)毛油真空脱水，真空脱气充氮后冷藏贮存；b)油脂存储、运输、加工装置采用不锈钢材质，在隔氧条件下进行精炼；c)控制精炼过程中所用水或蒸汽中氧、金属离子和氯离子的含量；d)成品油快速降温到35℃以下，并加入组合抗氧化剂。A method for improving the stability and safety of microbial oils and fats, by controlling the peroxide value, anisidine value, acid value, free fatty acid, moisture, and 3-chloropropanol content of microbial oils and fats to improve the stability and safety of microbial oils and fats , Characterized in that it includes the following aspects: a) vacuum dehydration of crude oil, vacuum degassing and nitrogen storage, and refrigerated storage; b) grease storage, transportation, and processing equipment using stainless steel and refining under oxygen-blocking conditions; c) controlled refining The content of oxygen, metal ions and chloride ions in the water or steam used in the process; d) The product oil is rapidly cooled to below 35 ° C, and a combined antioxidant is added.
  2. 根据权利要求1所述的提高微生物油脂稳定性和安全性的方法，其特征在于，在a)方面，所述毛油冷藏贮存的温度为0-10℃。The method for improving the stability and safety of microbial oils and fats according to claim 1, characterized in that, in aspect a), the temperature of the crude oil during cold storage is 0-10 ° C.
  3. 根据权利要求2所述的提高微生物油脂稳定性和安全性的方法，其特征在于，在a)方面，所述毛油冷藏贮存的温度为5-8℃。The method for improving the stability and safety of microbial oils and fats according to claim 2, characterized in that, in the aspect a), the temperature of the crude oil during cold storage is 5-8 ° C.
  4. 根据权利要求1所述的提高微生物油脂稳定性和安全性的方法，其特征在于，在b)方面，所述油脂的存储、运输、加工装置，包括所有用于精炼的反应釜、管道与阀门的材质为304L、316或316L不锈钢材质。The method for improving the stability and safety of microbial oils and fats according to claim 1, characterized in that, in aspect b), the storage, transportation, and processing devices for the oils and fats include all reaction kettles, pipes, and valves for refining The material is 304L, 316 or 316L stainless steel.
  5. 根据权利要求1所述的提高微生物油脂稳定性和安全性的方法，其特征在于，在b)方面，所述隔氧条件为抽真空隔绝氧氧气或者充氮隔绝氧气。The method for improving the stability and safety of microbial oils and fats according to claim 1, characterized in that, in aspect b), the oxygen-blocking condition is evacuating to isolate oxygen or nitrogen-filling to isolate oxygen.
  6. 根据权利要求1所述的提高微生物油脂稳定性和安全性的方法，其特征在于，在c)方面，所述控制精炼过程中所用水或蒸汽中氧、金属离子和氯离子的含量的方法中，所用水都是反渗透纯净水，水中游离氯含量≤0.05mg/L。The method for improving the stability and safety of microbial oils and fats according to claim 1, wherein, in aspect c), in the method for controlling the content of oxygen, metal ions and chloride ions in water or steam used in the refining process All the water is reverse osmosis purified water, and the free chlorine content in the water is ≤0.05mg / L.
  7. 根据权利要求1所述的提高微生物油脂稳定性和安全性的方法，其特征在于，在c)方面，所述控制精炼过程中所用水或蒸汽中氧、金属离子和氯离子的含量的方法中，汽提所用的蒸汽为经过脱氧处理的反渗透纯净水加热所得的蒸汽，蒸汽的管道采用316L或316材质的不锈钢管道。The method for improving the stability and safety of microbial oils and fats according to claim 1, wherein, in aspect c), in the method for controlling the content of oxygen, metal ions and chloride ions in water or steam used in the refining process The steam used for the stripping is the steam obtained by heating the reverse osmosis purified water after the deoxidation treatment. The steam pipe is made of 316L or 316 stainless steel pipe.
  8. 根据权利要求1所述的提高微生物油脂稳定性和安全性的方法，其特征在于，在d)方面，所述组合抗氧化剂为，维生素E、维生素C棕榈酸酯、卵磷脂和迷迭香中两种以上的组合物。The method for improving the stability and safety of microbial oils and fats according to claim 1, wherein, in aspect d), the combined antioxidant is vitamin E, vitamin C palmitate, lecithin, and rosemary A combination of two or more.
  9. 根据权利要求8所述的提高微生物油脂稳定性和安全性的方法，其特征在于，所述组合抗氧化剂为：The method for improving the stability and safety of microbial oils and fats according to claim 8, wherein the combined antioxidant is:
    维生素E1000-1500ppm和维生素C棕榈酸酯1000-1200ppm；Vitamin E1000-1500ppm and Vitamin C palmitate 1000-1200ppm;
    或者，维生素E1000-1500ppm、维生素C棕榈酸酯1000-1200ppm和卵磷脂5000ppm；Or, vitamin E1000-1500ppm, vitamin C palmitate 1000-1200ppm, and lecithin 5000ppm;
    或者，维生素E1000-1500ppm、维生素C棕榈酸酯1000-1200ppm和迷迭香1000-1200ppm。Alternatively, vitamin E 1000-1500 ppm, vitamin C palmitate 1000-1200 ppm, and rosemary 1000-1200 ppm.
  10. 根据权利要求1所述的提高微生物油脂稳定性和安全性的方法，其特征在于，在d)方面，所述成品油的3氯丙醇含量不高于200μg/kg，酸价以KOH计不超过0.8mg/g。The method for improving the stability and safety of microbial oils and fats according to claim 1, characterized in that, in aspect d), the content of 3chloropropanol in the product oil is not higher than 200 μg / kg, and the acid value is not in KOH More than 0.8mg / g.
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