CN116948744B - Corn oil moderate processing technology - Google Patents
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- 235000005687 corn oil Nutrition 0.000 title claims abstract description 137
- 239000002285 corn oil Substances 0.000 title claims abstract description 133
- 238000005516 engineering process Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 99
- 240000008042 Zea mays Species 0.000 claims abstract description 79
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 79
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 76
- 235000005822 corn Nutrition 0.000 claims abstract description 76
- 239000010779 crude oil Substances 0.000 claims abstract description 72
- 238000004332 deodorization Methods 0.000 claims abstract description 60
- 229930191978 Gibberellin Natural products 0.000 claims abstract description 24
- IXORZMNAPKEEDV-UHFFFAOYSA-N gibberellic acid GA3 Natural products OC(=O)C1C2(C3)CC(=C)C3(O)CCC2C2(C=CC3O)C1C3(C)C(=O)O2 IXORZMNAPKEEDV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003448 gibberellin Substances 0.000 claims abstract description 24
- 238000009874 alkali refining Methods 0.000 claims abstract description 8
- 239000011552 falling film Substances 0.000 claims abstract description 6
- MBMQEIFVQACCCH-UHFFFAOYSA-N trans-Zearalenon Natural products O=C1OC(C)CCCC(=O)CCCC=CC2=CC(O)=CC(O)=C21 MBMQEIFVQACCCH-UHFFFAOYSA-N 0.000 claims description 74
- MBMQEIFVQACCCH-QBODLPLBSA-N zearalenone Chemical compound O=C1O[C@@H](C)CCCC(=O)CCC\C=C\C2=CC(O)=CC(O)=C21 MBMQEIFVQACCCH-QBODLPLBSA-N 0.000 claims description 74
- 230000014759 maintenance of location Effects 0.000 claims description 41
- 230000001877 deodorizing effect Effects 0.000 claims description 35
- 239000003921 oil Substances 0.000 claims description 34
- 235000019198 oils Nutrition 0.000 claims description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 239000003463 adsorbent Substances 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 17
- 238000005086 pumping Methods 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000004927 clay Substances 0.000 claims description 12
- 235000013305 food Nutrition 0.000 claims description 12
- 238000007670 refining Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000008234 soft water Substances 0.000 claims description 11
- 241000196324 Embryophyta Species 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 150000002576 ketones Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000344 soap Substances 0.000 claims description 6
- 238000010306 acid treatment Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 23
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 124
- -1 trichloropropanol ester Chemical class 0.000 description 64
- 239000000194 fatty acid Substances 0.000 description 42
- 235000014113 dietary fatty acids Nutrition 0.000 description 37
- 229930195729 fatty acid Natural products 0.000 description 37
- 150000004665 fatty acids Chemical class 0.000 description 37
- 238000004519 manufacturing process Methods 0.000 description 31
- 239000002994 raw material Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 18
- 235000002378 plant sterols Nutrition 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229930003427 Vitamin E Natural products 0.000 description 7
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 7
- 229940046009 vitamin E Drugs 0.000 description 7
- 235000019165 vitamin E Nutrition 0.000 description 7
- 239000011709 vitamin E Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000004519 grease Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LAMUXTNQCICZQX-UHFFFAOYSA-N 3-chloropropan-1-ol Chemical compound OCCCCl LAMUXTNQCICZQX-UHFFFAOYSA-N 0.000 description 4
- 244000052616 bacterial pathogen Species 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000008157 edible vegetable oil Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 235000009973 maize Nutrition 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 210000001161 mammalian embryo Anatomy 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000556 factor analysis Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000021049 nutrient content Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C11B3/00—Refining fats or fatty oils
- C11B3/02—Refining fats or fatty oils by chemical reaction
- C11B3/04—Refining fats or fatty oils by chemical reaction with acids
-
- 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
- C11B3/02—Refining fats or fatty oils by chemical reaction
- C11B3/06—Refining fats or fatty oils by chemical reaction with bases
-
- 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
-
- 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
- C11B3/12—Refining fats or fatty oils by distillation
- C11B3/14—Refining fats or fatty oils by distillation with the use of indifferent gases or vapours, e.g. steam
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention relates to a moderate processing technology of corn oil, which belongs to the technical field of corn oil processing and comprises the procedures of degumming, alkali refining deacidification, decoloring, dewaxing and deodorization, wherein the decoloring procedure carries out graded control on technological conditions according to the content of corn crude gibberellic ketene, the deodorization adopts a double-tower technology, a deodorization tower 1 is a laminate tower, the graded control on technological conditions are carried out according to the content of corn crude gibberellic ketene in the control deodorization tower 1, and a deodorization tower 2 is a falling film tower; the invention solves the contradiction point that the other corresponding indexes are negatively affected only for one or a plurality of corn oil indexes in the prior art by closely matching the process steps, particularly carrying out the grading control of the process according to the different content of the corn crude oil and the corn gibberellin, realizes the purpose of keeping the beneficial components in the corn oil and simultaneously can reduce the content of harmful components in the corn oil so as to achieve a good balance point between the components.
Description
Technical Field
The invention relates to the technical field of corn oil refining processes, in particular to a moderate corn oil processing process.
Background
In recent years, the edible oil consumption in China has a consumption error area, and the appearance indexes such as light color, less oil smoke and the like are excessively required, so that the content of nutritional ingredients in the edible vegetable oil, such as the content of oil-soluble vitamin E and phytosterol in corn oil, is ignored. The crude oil contains natural vitamin E (600-1000 mg/kg) and natural plant sterol (8000-12000 ug/kg). In the refining process of corn oil, if the pursuing color of the flavor is light, the smoke point is high, and the factors such as long time, high temperature and the like in the processing process can cause the almost complete loss of natural vitamin E and natural plant sterols in the corn oil, and simultaneously, trans-fatty acid, trichloropropanol ester, glycidyl ester and the like which are harmful to human bodies can be generated.
In the prior art, in the ' measurement and removal of zearalenone in corn oil ' of the university of Jiangnan's Lavender paper in 2017, the removal effect of an alkali refining method and an ultraviolet irradiation method on zearalenone in corn oil is disclosed. The patent application with publication number of CN109609264A discloses a refining process for improving the quality of corn oil, which comprises the steps of balancing the acid value of crude oil of the corn oil, alkali refining, dewaxing, decoloring, filtering, deodorizing and the like which are sequentially carried out. The method aims to solve the problems of toxin pollution caused by corn raw materials, reduced VE content and sterol content, increased trans-fatty acid and the like caused by excessive refining, so that the high-quality corn oil with stable nutrient content and low harmful components is obtained.
However, in the refining process of vegetable oil and fat, 3-chloropropanol ester and glycidyl ester are also generated due to the excessively high refining temperature, and the two substances become novel vegetable oil pollutants which are concerned worldwide and have potential harm to human bodies. The patent application with publication number of CN112725082A discloses a method for removing 3-chloropropanol ester and glycidyl ester in grease, which takes corn oil processing enterprises to degumm, deacidify and decolor by a conventional method to obtain corn oil to be deodorized as a processing object, pre-deodorizes the grease by taking water vapor as a deodorization medium, adsorbs the grease by taking modified clay (a compound of activated clay and calcium polysilicate) as an adsorbent, and finally performs deodorization again by taking the water vapor as the deodorization medium. Although the method can obviously reduce the content of 3-chloropropanol and glycidyl ester in the grease, the removal rate of harmful substances zearalenone in the grease is greatly reduced, and the loss of vitamin E is larger. Therefore, balancing the harmful substances and beneficial substances in corn oil is a technical problem which is difficult to solve at present.
Therefore, the application aims to solve the technical problems of keeping beneficial components vitamin E and natural plant sterols in corn oil, reducing the content of harmful components zearalenone in the corn oil and reducing the production of harmful components trans fatty acid, 3-chloropropanol, glycidyl ester and the like in the processing process so as to achieve good balance points among the components.
Disclosure of Invention
The application provides a corn oil moderate processing technology aiming at the problems in the prior art, which aims to solve the technical problems that: the corn oil has the beneficial components of vitamin E and natural plant sterol maintained, and can reduce the content of zearalenone as harmful component, reduce the production of trans fatty acid, 3-chloropropanol and glycidyl ester as new harmful component in the processing process, and reach good balance point between the components.
The technical scheme for solving the technical problems is as follows: a corn oil moderate processing technology is characterized by comprising the following steps:
(1) Degumming: heating corn crude oil to 60 ℃, adding 85% food grade phosphoric acid, wherein the dosage of the food grade phosphoric acid is 0.05% of that of the corn crude oil, performing acid treatment, and then washing the crude oil by adopting chlorine-free soft water;
(2) Alkali refining deacidification: the degummed corn oil reacts with liquid alkali (food grade), and then the corn oil is washed by adopting chlorine-free soft water until the residual soap in the corn oil is less than 300mg/kg;
(3) Decoloring: pumping the deacidified corn oil into a decoloring tower for decoloring, controlling the decoloring time at 110-120 ℃ to control the content of zearalenone in the decolored corn oil within the following range:
when the content of zearalenone in the crude maize oil is more than 5000ug/kg, controlling the content of zearalenone in the decolored maize oil to be not higher than 1500ug/kg;
when the content of zearalenone in the crude corn oil is 3000-5000ug/kg, controlling the content of zearalenone in the decolorized corn oil to be not higher than 1000ug/kg;
when the content of zearalenone in crude corn oil is less than 3000ug/kg, controlling the content of zearalenone in decolorized corn oil to be not higher than 800ug/kg;
the dosage of the decoloring agent is 0.5-5% of that of corn oil, the decoloring agent adopts a mixture of activated clay and plant active carbon, wherein the addition amount of the plant active carbon accounts for 10-20% of that of the activated clay;
filtering the decoloring agent to obtain a dehydrated oil;
(4) Dewaxing: pumping the decolorized oil into a gradient cooling multi-stage crystallization tank, and growing crystals (precipitating wax); separating dewaxed corn oil;
(5) Deodorizing: the double-tower process is adopted, and the concrete steps are as follows:
the deodorization tower 1 is a laminate tower, and the process conditions in the deodorization tower 1 are controlled as follows:
when the corn crude oil gibberellin ketone is more than 5000ug/kg, the temperature of the deodorization tower 1 is controlled at 240 ℃, the retention time is controlled at 50 minutes, and the direct steam pressure is 0.03Mpa;
when corn crude oil gibberellin ketone is 3000-5000ug/kg, the temperature of the deodorization tower 1 is controlled at 235 ℃, the retention time is controlled at 40 minutes, and the direct steam pressure is 0.03Mpa;
when the corn crude oil gibberellin ketone is less than 3000ug/kg, the temperature of the deodorization tower 1 is controlled at 230 ℃, the retention time is controlled at 30 minutes, and the direct steam pressure is 0.03Mpa;
the deodorizing tower 2 is a falling film tower, the deodorizing temperature is controlled to be 190-220 ℃, and the retention time is controlled to be 30 minutes.
Further comprises the following steps of (6) refining post-treatment: and (3) re-adsorbing the deodorized corn oil by using an adsorbent under the condition that the residual pressure is less than 1000 kilopascals and the temperature is 120-127 ℃, wherein the using amount of the adsorbent is 0.2-0.5% of that of the corn oil, and the adsorbent is diatomite.
Further, the storage temperature of the raw corn germ for producing the corn crude oil is not higher than 30 ℃.
Further, the drying treatment of the raw material corn germ for producing the corn crude oil is as follows: drying the corn germ at a drying temperature below 130deg.C (preferably 90-130deg.C) until the moisture content is below 9%.
Further, the step (2): the degummed corn oil reacts with liquid alkali (food grade), and then the corn oil is washed by adopting chlorine-free soft water until the residual soap in the corn oil is less than 300mg/kg; the concentration of the liquid alkali used is 16 Baume degrees, and the super alkali content is 20 percent.
In the dewaxing step (4), decolorizing oil is pumped into a mixing tank, then filter aid diatomite is added, and the mixture is stirred uniformly and pumped into a gradient cooling multistage crystallization tank. The cooling rate in the gradient cooling process is as follows: the temperature is reduced to 15 ℃ at 30 ℃ for 4 hours, and the temperature is reduced to 10 ℃ at 15 ℃ for 4 hours; the temperature is reduced to 5 ℃ from 10 ℃ and the time is 3 hours; raising the temperature to 7 ℃ at 5 ℃ for 1 hour; the total time of crystal growing is about 12 hours. The gradient cooling process, especially the one hour tempering in the last step, is distinguished from the conventional process of the prior art in that the step operation facilitates filtration of corn oil. And (3) after the temperature reaches 7-8 ℃, feeding the corn oil into a vane filter, and separating dewaxed corn oil.
Further, the dewaxing step of the step (4) is carried out at the temperature of 18-25 ℃.
The beneficial effects of the invention are as follows: the invention provides a moderate processing technology of corn oil, which solves the contradiction point that the other corresponding indexes are negatively affected only for one or a plurality of corn oil indexes in the prior art by closely matching the process steps, particularly carrying out grading control on the process according to the different content of corn crude oil corn gibberellin, realizes the effects of keeping beneficial components vitamin E and natural plant sterol in corn oil, reducing the content of harmful components corn gibberellin in the corn oil, reducing the production of harmful components trans fatty acid, 3-chloropropanol, glycidyl ester and the like in the processing process, ensures that the components reach good balance point, improves the quality of edible oil, reduces the waste of energy, improves the refining rate and saves social resources.
Detailed Description
The principles and features of the present invention are described below with examples provided for the purpose of illustration only and are not intended to limit the scope of the invention.
The corn germ used in the embodiments of the invention has the content of the zearalenone of 2000-8000ug/kg detected, and the storage temperature of the corn germ is not higher than 30 ℃. Classifying according to quality indexes of corn germ raw materials, and classifying according to the content of zearalenone in corn germs, wherein the classifying processing is carried out according to three grades, and the three grades are respectively: the zearalenone is higher than 5000ug/kg, the zearalenone is between 3000 and 5000ug/kg, and the zearalenone is less than 3000ug/kg. The obtained crude corn oil is stored according to the content of zearalenone in separate tanks; the corn germ raw materials with similar quality grades are continuously processed for no less than 24 hours.
First, corn crude oil is prepared from the above raw material corn germ:
and (3) production and feeding: after the maize germs are discharged from the temporary storage bin, removing impurities and iron from the maize germs; cleaning the screen and the magnet at regular intervals;
softening and squeezing embryo: the softening temperature of the maize germs is 75 ℃;
steaming and parching: steaming and parching corn embryo at 90-110deg.C, and adjusting water content to below 9%;
Oil extraction: adopting a spiral oil press to press oil, and controlling the oil pressing temperature below 130 ℃;
leaching: the pressed corn cake is leached by solvent, evaporated by an evaporator and stripped by a stripping tower to obtain corn crude oil, and the temperature of the stripping tower is controlled below 130 ℃.
Corn oil was then produced in the manner of the following examples with the corn crude oil produced.
Example 1:
the corn crude oil with the content of the zearalenone higher than 5000ug/kg is used as a raw material, and the corn oil moderate processing technology is provided, and comprises the following steps:
(1) Degumming: heating corn crude oil to 60 ℃, adding 85% food grade phosphoric acid, wherein the dosage of the food grade phosphoric acid is 0.05% of that of the corn crude oil, the acid reaction time is 40 minutes, performing acid treatment, and then washing the crude oil by adopting chlorine-free soft water;
(2) Alkali refining deacidification: the degummed corn oil reacts with liquid alkali, the concentration of the liquid alkali is 16 Baume degrees, the super alkali amount is 20%, the alkali reaction time is controlled to be about 30 minutes, and then the corn oil is washed by adopting chlorine-free soft water until the residual soap in the corn oil is less than 100mg/kg;
(3) Decoloring: pumping the deacidified corn oil into a decoloring tower for decoloring, wherein the decoloring temperature is 120 ℃, and the decoloring time is controlled so that the content of zearalenone in the decolored corn oil is not higher than 1500ug/kg;
The dosage of the decoloring agent is 5% of that of corn oil, the decoloring agent adopts a mixture of activated clay and plant active carbon, wherein the addition of the plant active carbon accounts for 20% of that of the activated clay;
filtering the decoloring agent to obtain a dehydrated oil;
(4) Dewaxing: pumping the decolorized oil into a mixing tank, adding filter aid diatomite, uniformly stirring, and pumping into a gradient cooling multistage crystallization tank, wherein the cooling rate of gradient cooling is as follows: the temperature is reduced to 15 ℃ at 30 ℃ for 4 hours, and the temperature is reduced to 10 ℃ at 15 ℃ for 4 hours; the temperature is reduced to 5 ℃ from 10 ℃ and the time is 3 hours; raising the temperature to 7 ℃ at 5 ℃ for 1 hour; pumping into a filter to separate oil from wax after the temperature is raised to 7 ℃ to separate dewaxed corn oil; the dewaxing process is carried out at the temperature of 18-25 ℃ and the equipment and the pipelines are insulated, and the dewaxing production area is relatively isolated from other areas of the workshop;
(5) Deodorizing: the double-tower process is adopted, and the concrete steps are as follows:
the deodorization tower 1 is a laminate tower, the temperature of the deodorization tower 1 is controlled to be 240 ℃, the residual pressure is less than 300 Pa, the retention time is controlled to be about 50 minutes, and the direct steam pressure is controlled to be 0.03MPa;
the deodorization tower 2 is a falling film tower, the deodorization temperature is controlled to be 220 ℃, the residual pressure is less than 300 Pa, the retention time is controlled to be about 30 minutes, and the direct steam pressure is controlled to be 0.03MPa.
(6) Refining post-treatment: re-adsorbing the deodorized corn oil by using an adsorbent under the conditions that the pressure is less than 1000 kilopascals and the temperature is 120 ℃, wherein the adsorbent adopts diatomite, and the using amount of the adsorbent is 0.5% of that of the corn oil; separating the adsorbent by using a leaf filter;
and finally, filling high-purity nitrogen inert gas into the finished oil tank, expelling air at the top of the oil tank, stabilizing the quality of the first-stage corn oil, and achieving the effect of prolonging the shelf life. The bottom of the finished oil tank is periodically supplemented with nitrogen every week later, and the oxygen is isolated by keeping the inert gas in the finished oil and at the top of the oil tank.
Example 2:
the corn crude oil with the zearalenone content of 3000-5000ug/kg is taken as a raw material, and the corn oil moderate processing technology is provided, which comprises the following steps:
(1) Degumming: heating corn crude oil to 60 ℃, adding 85% food grade phosphoric acid, wherein the dosage of the food grade phosphoric acid is 0.05% of that of the corn crude oil, the acid reaction time is 40 minutes, performing acid treatment, and then washing the crude oil by adopting chlorine-free soft water;
(2) Alkali refining deacidification: the degummed corn oil reacts with liquid alkali, the concentration of the liquid alkali is 16 Baume degrees, the super alkali amount is 20%, the alkali reaction time is controlled to be about 30 minutes, and then the corn oil is washed by adopting chlorine-free soft water until the residual soap in the corn oil is less than 100mg/kg;
(3) Decoloring: pumping the deacidified corn oil into a decoloring tower for decoloring, wherein the decoloring temperature is 115 ℃, and the decoloring time is controlled so that the content of zearalenone in the decolored corn oil is not higher than 1000ug/kg;
the dosage of the decoloring agent is 3% of that of corn oil, the decoloring agent adopts a mixture of activated clay and plant active carbon, wherein the addition of the plant active carbon accounts for 15% of that of the activated clay;
filtering the decoloring agent to obtain a dehydrated oil;
(4) Dewaxing: pumping the decolorized oil into a mixing tank, adding filter aid diatomite, uniformly stirring, and pumping into a gradient cooling multistage crystallization tank, wherein the cooling rate of gradient cooling is as follows: the temperature is reduced to 15 ℃ at 30 ℃ for 4 hours, and the temperature is reduced to 10 ℃ at 15 ℃ for 4 hours; the temperature is reduced to 5 ℃ from 10 ℃ and the time is 3 hours; raising the temperature to 7 ℃ at 5 ℃ for 1 hour; pumping into a filter to separate oil from wax after the temperature is raised to 7 ℃ to separate dewaxed corn oil; the dewaxing process is carried out at the temperature of 18-25 ℃ and the equipment and the pipelines are insulated, and the dewaxing production area is relatively isolated from other areas of the workshop;
(5) Deodorizing: the double-tower process is adopted, and the concrete steps are as follows:
the deodorization tower 1 is a laminate tower, the deodorization temperature is controlled to be 235 ℃, the residual pressure is less than 300 Pa, the retention time is controlled to be about 40 minutes, and the direct steam pressure is controlled to be 0.03MPa;
The deodorization tower 2 is a falling film tower, the deodorization temperature is controlled at 210 ℃, the residual pressure is less than 300 Pa, the retention time is controlled at about 30 minutes, and the direct steam pressure is 0.03MPa.
(6) Refining post-treatment: re-adsorbing the deodorized corn oil by using an adsorbent under the conditions that the pressure is less than 1000 kilopascals and the temperature is 120 ℃, wherein the adsorbent adopts diatomite, and the usage amount of the adsorbent is 0.2% of that of the corn oil; separating the adsorbent by using a leaf filter;
and finally, filling high-purity nitrogen inert gas into the finished oil tank, expelling air at the top of the oil tank, stabilizing the quality of the first-stage corn oil, and achieving the effect of prolonging the shelf life. The bottom of the finished oil tank is periodically supplemented with nitrogen every week later, and the oxygen is isolated by keeping the inert gas in the finished oil and at the top of the oil tank.
Example 3:
the corn crude oil with the content of the zearalenone less than 3000ug/kg is taken as a raw material, and the corn oil moderate processing technology is provided, which comprises the following steps:
(1) Degumming: heating corn crude oil to 60 ℃, adding 85% food grade phosphoric acid, wherein the dosage of the food grade phosphoric acid is 0.05% of that of the corn crude oil, the acid reaction time is 40 minutes, performing acid treatment, and then washing the crude oil by adopting dechlorinated soft water;
(2) Alkali refining deacidification: the degummed corn oil reacts with liquid alkali, the concentration of the liquid alkali is 16 Baume degrees, the super alkali amount is 20%, the alkali reaction time is controlled to be about 30 minutes, and then the corn oil is washed by adopting chlorine-free soft water until the residual soap in the corn oil is less than 300mg/kg;
(3) Decoloring: pumping the deacidified corn oil into a decoloring tower for decoloring, wherein the decoloring temperature is 110 ℃, and the decoloring time is controlled so that the content of zearalenone in the decolored corn oil is not higher than 800ug/kg;
the dosage of the decoloring agent is 0.5% of that of corn oil, the decoloring agent adopts a mixture of activated clay and plant active carbon, wherein the addition of the plant active carbon accounts for 10% of that of the activated clay;
filtering the decoloring agent to obtain a dehydrated oil;
(4) Dewaxing: pumping the decolorized oil into a mixing tank, adding filter aid diatomite, uniformly stirring, and pumping into a gradient cooling multistage crystallization tank, wherein the cooling rate of gradient cooling is as follows: the temperature is reduced to 15 ℃ at 30 ℃ for 4 hours, and the temperature is reduced to 10 ℃ at 15 ℃ for 4 hours; the temperature is reduced to 5 ℃ from 10 ℃ and the time is 3 hours; raising the temperature to 7 ℃ at 5 ℃ for 1 hour; pumping into a filter to separate oil from wax after the temperature is raised to 7 ℃ to separate dewaxed corn oil; the dewaxing process is carried out at the temperature of 18-25 ℃ and the equipment and the pipelines are insulated, and the dewaxing production area is relatively isolated from other areas of the workshop;
(5) Deodorizing: the double-tower process is adopted, and the concrete steps are as follows:
the deodorization tower 1 is a laminate tower, the deodorization temperature is controlled at 230 ℃, the residual pressure is less than 300 Pa, the retention time is controlled at about 30 minutes, and the direct steam pressure is 0.03MPa;
the deodorization tower 2 is a falling film tower, the deodorization temperature is controlled to be 190 ℃, the residual pressure is less than 300 Pa, the retention time is controlled to be about 30 minutes, and the direct steam pressure is controlled to be 0.03MPa.
(6) Refining post-treatment: re-adsorbing the deodorized corn oil by using an adsorbent under the conditions that the pressure is less than 1000 kilopascals and the temperature is 120 ℃, wherein the adsorbent adopts diatomite, and the usage amount of the adsorbent is 0.2% of that of the corn oil; separating the adsorbent by using a leaf filter;
and finally, filling high-purity nitrogen inert gas into the finished oil tank, expelling air at the top of the oil tank, stabilizing the quality of the first-stage corn oil, and achieving the effect of prolonging the shelf life. The bottom of the finished oil tank is periodically supplemented with nitrogen every week later, and the oxygen is isolated by keeping the inert gas in the finished oil and at the top of the oil tank.
Comparative example 1:
the raw materials and the process of this comparative example were substantially the same as in example 1, except that the temperature of the deodorizing tower 1 was 250 ℃.
Table 1 comparative example 1 and example 1 data statistics table
The procedure for the production of corn oil of comparative example 1 was essentially the same as that of corn crude oil of example 1 except that the temperature of the deodorizing tower 1 used in comparative example 1 was different from that used in example 1, and according to the analysis of the results, when the corn crude oil content of gibberellin was 5000mg/kg or more, the temperature of the tower 1 was used: 250 ℃; time: 50 minutes; vacuum degree: 250 Pa; the direct steam pressure is 0.03Mpa under the process conditions:
the reduction of zearalenone in comparative example 1 to 95ug/kg reduced the zearalenone content by 85ug/kg compared to example 1;
the 3-chloropropanol ester and the glycidyl ester in comparative example 1 were 1890ug/kg and 1260ug/kg, respectively, which were increased as compared with example 1 by 975ug/kg and 430ug/kg, respectively;
the trans fatty acid content in comparative example 1 was 2.52%, and the increase was significant, 1.32% as compared to the trans fatty acid content of 1.20% in example 1;
the VE content in comparative example 1 was 5.5mg/100g, which was significantly reduced by 16mg/100g as compared to the VE content of 21.5mg/100g in example 1;
the plant sterol content in comparative example 1 was 1505ug/kg, and the reduction was remarkable and 5345ug/kg was reduced as compared with the plant sterol content of 6850ug/kg in example 1.
The method shows that when the content of zearalenone in crude oil is high, the temperature of the deodorization tower 1 is high (250 ℃), the temperature of corn oil in the deodorization tower 1 is too high, the decomposition of the harmful component zearalenone in the processing process is increased, the content is correspondingly reduced, and the increase of the harmful component trans-fatty acid is obvious; however, the production of 3-chloropropanol ester and glycidyl ester, which are harmful components, is greatly increased. Meanwhile, the deodorizing temperature is too high, the influence on the reduction of the retention of the beneficial component VE is remarkable, and the influence on the reduction of the retention of the phytosterol is remarkable; the temperature has little effect on the acid value.
Comparative example 2:
the raw materials and the process of this comparative example were substantially the same as in example 1, except that the temperature of the deodorizing tower 1 was 235 ℃.
Table 2 comparative example 2 and example 2 data statistics table
The procedure for the production of corn oil of comparative example 2 was essentially the same as that of corn crude oil of example 1 except that the temperature of the deodorizing tower 1 used in comparative example 1 was different from that used in example 1, and according to the analysis of the results, when the corn crude oil content of gibberellin was 5000mg/kg or more, the temperature of the tower 1 was used: 235 ℃; time: 50 minutes; vacuum degree: 250 Pa; the direct steam pressure is 0.03Mpa under the process conditions:
The content of zearalenone in comparative example 2 is increased to 215ug/kg, and the increase is not obvious compared with that in example 1 by 35 ug/kg;
the 3-chloropropanol ester and the glycidyl ester in comparative example 2 were 850ug/kg and 796ug/kg, respectively, which were reduced by 65ug/kg and 34ug/kg, respectively, as compared with example 1;
the trans fatty acid content in comparative example 2 was 1.05%, and the decrease was not significant, but was 0.15% as compared with the trans fatty acid content of 1.20% in example 1;
the VE content in comparative example 2 was 23.5mg/100g, which was not significantly increased by 2.0mg/100g as compared to the VE content of 21.5mg/100g in example 1;
the phytosterol content in comparative example 2 was 6950ug/kg, which was instead increased by 100ug/kg, and the increase was insignificant, compared to 6850ug/kg in example 1.
The method shows that when the content of the zearalenone in crude oil is high, the temperature of the deodorization tower 1 is low (235 ℃), the temperature of the corn oil in the deodorization tower is too low, the decomposition of the harmful component zearalenone in the processing process is reduced, and the content increase range is limited; the reduction of the trans fatty acid of the harmful component is not obvious; the production amount of the harmful components of 3-chloropropanol ester and glycidyl ester is reduced, and the reduction amount is not obvious; meanwhile, when the deodorization temperature is higher, the temperature is reduced, the influence on the increase of the VE retention of the beneficial component is not obvious, the retention of the phytosterol is increased, and the influence is not obvious; the temperature has little effect on the acid value.
Comparative example 3:
the raw materials and the process of this comparative example were substantially the same as in example 2, except that the temperature of the deodorizing tower 1 was 240 ℃.
Table 3 comparative example 3 and example 3 data statistics table
The procedure for the production of corn oil of comparative example 3 was substantially the same as that of corn crude oil of example 2 except that the temperature of the deodorizing tower 1 used in comparative example 3 was different from that used in example 2, and according to the analysis of the result, when the corn crude oil contains 4600mg/kg of gibberellin, the temperature of the tower 1 was used: 240 ℃; time: 40 minutes; vacuum degree: 250 Pa; the direct steam pressure is 0.03Mpa under the process conditions:
the reduction of zearalenone in comparative example 3 to 95ug/kg is less pronounced than the reduction of zearalenone in example 2 by 30 ug/kg;
the 3-chloropropanol ester and the glycidyl ester in comparative example 3 were 1256ug/kg and 1035ug/kg, respectively, which were increased as compared with example 2 by 271ug/kg and 157ug/kg, respectively; the 3-chloropropanol ester and the glycidyl ester in the comparative example 3 exceed the quality limit index of the enterprise control;
the trans fatty acid content in comparative example 3 was 0.75%, and the increase was not significant, but 0.05% as compared with the trans fatty acid content of 0.70% in example 2;
The VE content in comparative example 3 was 18.0mg/100g, which was significantly reduced by 5.0mg/100g as compared to the VE content of 23.0mg/100g in example 2;
the phytosterol content in comparative example 3 was 5430ug/kg, which was significantly reduced by 1585ug/kg compared to 7015ug/kg in example 2.
The method shows that when the content of the zearalenone in crude oil is moderate, the temperature of the deodorization tower 1 is higher (240 ℃), the temperature of the corn oil in the deodorization tower is too high, the decomposition of the harmful component zearalenone in the processing process is increased, and the content reduction range is limited; the increase of the trans fatty acid of the harmful component is not obvious; but the production amount of the harmful components 3-chloropropanol ester and glycidyl ester is increased, the increase amount is obvious, and the index exceeds the index of the inner control limit value of an enterprise; meanwhile, when the deodorization temperature is higher, the temperature is increased, and the influence on the reduction of the retention quantity of the beneficial component VE is remarkable; the retention of the phytosterol is reduced, and the influence is obvious; the temperature has little effect on the acid value.
Comparative example 4:
the raw materials and the process of this comparative example were substantially the same as in example 2, except that the temperature of the deodorizing tower 1 was 230 ℃.
Table 4 data statistics table for comparative example 4 and example 2
The procedure for the production of corn oil of comparative example 4 was substantially the same as that of corn crude oil of example 2 except that the temperature of the deodorizing tower 1 used in comparative example 4 was different from that used in example 2, and according to the analysis of the result, when the corn crude oil contains 4600mg/kg of gibberellin, the temperature of the tower 1 was used: 230 ℃; time: 40 minutes; vacuum degree: 250 Pa; the direct steam pressure is 0.03Mpa under the process conditions:
The content of zearalenone in comparative example 4 is reduced to 235ug/kg, and the content of zearalenone in comparative example 2 is increased by 110ug/kg, and the increase is obvious;
the 3-chloropropanol ester and the glycidyl ester in the comparative example 4 are 838ug/kg and 646ug/kg respectively, which are respectively reduced by 147ug/kg and 232ug/kg compared with the example 2, and the reduction effect is obvious;
the trans fatty acid content in comparative example 4 was 0.65%, which was reduced by 0.05% compared to the trans fatty acid content of 0.70% in example 2;
the VE content of comparative example 4 was 27.0mg/100g, which was significantly increased by 4.0mg/100g as compared to the VE content of 23.0mg/100g in example 2;
the phytosterol content in comparative example 4 was 7305ug/kg, which was increased by 290ug/kg as compared to 7015ug/kg in example 2.
The method shows that when the content of the zearalenone in crude oil is moderate, the temperature of the deodorization tower 1 is higher (230 ℃), the temperature of the corn oil in the deodorization tower is too low, the decomposition of the harmful component zearalenone in the processing process is reduced, and the content increase range is obvious; the content of the harmful component trans fatty acid is reduced, and the reduction is not obvious; the production amount of the harmful components 3-chloropropanol ester and glycidyl ester is reduced, and the reduction amount is obvious; meanwhile, when the deodorization temperature is higher, the temperature is reduced, and the retention amount of the plant sterol serving as a beneficial component is increased; the retention of the beneficial component VE is increased, and the influence is obvious; the temperature has little effect on the acid value.
Comparative example 5:
the raw materials and the process of this comparative example were substantially the same as in example 3, except that the temperature of the deodorizing tower 1 was 235 ℃.
Table 5 comparative example 5 and example 3 data statistics table
The procedure for the production of corn oil of comparative example 5 was substantially the same as that of corn crude oil of example 3 except that the temperature of the deodorizing tower 1 used in comparative example 5 was different from that used in example 3, and according to the analysis of the result, when the corn crude oil contains gibberellin at 1700mg/kg, the temperature of the tower 1 was used: 235 ℃; time: 30 minutes; vacuum (residual pressure): 250 Pa; the direct steam pressure is 0.03Mpa under the process conditions:
the reduction of zearalenone in comparative example 5 to 75ug/kg is less pronounced than the reduction of zearalenone in example 3 by 10 ug/kg;
the 3-chloropropanol ester and the glycidyl ester in the comparative example 5 are 836ug/kg and 703ug/kg respectively, which are increased compared with the example 3, 411ug/kg and 347ug/kg respectively, and the increase amplitude is obvious;
the trans fatty acid content in comparative example 5 was 0.65%, which is increased by 0.05% and the increase was not large, compared with the trans fatty acid content of 0.60% in example 3;
The VE content in comparative example 5 was 22.5mg/100g, which was significantly reduced by 5.5mg/100g as compared to the VE content of 28.0mg/100g in example 3;
the phytosterol content in comparative example 5 was 7430ug/kg, and the phytosterol content was significantly reduced, 1520ug/kg, as compared with 8950ug/kg in example 3.
The method shows that when the content of the zearalenone in crude oil is moderate, the temperature of the deodorization tower 1 is higher (235 ℃), the temperature of the corn oil in the deodorization tower is too high, the decomposition of the harmful component zearalenone in the processing process is increased, and the content reduction amplitude is not obvious; the content of the harmful component trans fatty acid is increased, and the increase is not obvious; however, the production amount of the harmful components 3-chloropropanol ester and glycidyl ester is increased, and the increase amount is obvious; meanwhile, the temperature in the deodorizing tower is too high, so that the retention amount of the plant sterol serving as a beneficial component is reduced, and the influence is obvious; the retention of the beneficial component VE is reduced, and the influence is obvious; the temperature has little effect on the acid value.
Comparative example 6:
the raw materials and the process of this comparative example were substantially the same as in example 3, except that the temperature of the deodorizing tower 1 was 225 ℃.
Table 6 comparative example 6 and example 3 data statistics table
The procedure for the production of corn oil of comparative example 6 was substantially the same as that of corn crude oil of example 3 except that the temperature of the deodorizing tower 1 used in comparative example 6 was different from that used in example 3, and according to the analysis of the result, when the corn crude oil contains gibberellin at 1700mg/kg, the temperature of the tower 1 was used: 225 ℃; time: 30 minutes; vacuum (residual pressure): 250 Pa; the direct steam pressure is 0.03Mpa under the process conditions:
The content of zearalenone in comparative example 6 is increased to 185ug/kg, and the content of zearalenone in comparative example 3 is increased by 100ug/kg, so that the increase is obvious;
the 3-chloropropanol ester and the glycidyl ester in comparative example 6 are 405ug/kg and 335ug/kg respectively, which are reduced by 20ug/kg and 21ug/kg respectively compared with the embodiment 3, and the reduction amplitude is not obvious;
the trans fatty acid content in comparative example 6 was 0.52%, which was reduced by 0.08% and the reduction was not large, compared with the trans fatty acid content of 0.60% in example 3;
the VE content in comparative example 6 was 31.0mg/100g, which was not significantly increased by 3.0mg/100g as compared to the VE content of 28.0mg/100g in example 3;
the phytosterol content in comparative example 6 was 8765ug/kg, and compared with 8950ug/kg in example 3, the phytosterol content was not increased, but was reduced by 185ug/kg, with a small reduction.
The method shows that when the content of the zearalenone in crude oil is smaller, the lower the temperature of the deodorization tower 1 is (225 ℃), the lower the temperature of the corn oil in the deodorization tower is, the less the decomposition of the harmful component zearalenone in the processing process is, the content is increased, and the amplitude is obvious; the content of trans fatty acid in harmful components is reduced, and the reduction amplitude is not obvious; however, the production amount of the harmful components of 3-chloropropanol ester and glycidyl ester is reduced, and the reduction amount is not obvious; meanwhile, when the deodorization temperature is lower, the temperature is reduced, and the influence on the retention amount of the plant sterol serving as the beneficial component is not obvious; the retention of the beneficial component VE is increased, and the influence is not obvious; the temperature has little effect on the acid value.
Comparative example 7:
the raw materials and the process of this comparative example were substantially the same as in example 1, except that the residence time in the deodorizing tower 1 was 40 minutes.
Table 7 comparative example 7 and example 1 data statistics table
The procedure for the production of corn oil of comparative example 7 was essentially the same as that of corn crude oil of example 1 except that the retention time in the deodorizing tower 1 used in comparative example 7 was different, and according to the analysis of the result, when the corn crude oil contains gibberellin at 5800mg/kg, the temperature of the tower 1 was used: 240 ℃; time: 40 minutes; vacuum (residual pressure): 250 Pa; the direct steam pressure is 0.03Mpa under the process conditions:
the zearalenone in comparative example 7 was increased to 225ug/kg, which was 45ug/kg greater than that in example 1;
the 3-chloropropanol ester and the glycidyl ester in comparative example 7 were 693ug/kg and 567ug/kg, respectively, which were reduced by 222ug/kg and 263ug/kg, respectively, as compared with example 1;
the trans fatty acid content in comparative example 7 was 0.72%, and the reduction was greater than the reduction of the trans fatty acid content of 1.20% in example 1 by 0.48%;
the VE content in comparative example 7 was 29.8mg/100g, which was increased by 8.3mg/100g as compared to the VE content in example 1;
The phytosterol content in comparative example 7 was 7538ug/kg, which was 688ug/kg increased as compared to the phytosterol content in example 1.
The corn oil has shorter residence time in the deodorization tower 1 when the content of the zearalenone in the crude oil is higher, the decomposition of the harmful component zearalenone in the processing process is reduced, and the content is increased; however, the production of trans fatty acid, 3-chloropropanol ester and glycidyl ester which are harmful components is also reduced; meanwhile, the shorter the deodorization residence time is, the larger the retention amount of the beneficial component VE and the plant sterol is; the temperature has little effect on the acid value.
Comparative example 8:
the raw materials and the process of this comparative example were substantially the same as in example 1, except that the residence time in the deodorizing tower 1 was 60 minutes.
Table 8 comparative example 8 and example 1 data statistics table
The procedure for the production of corn oil of comparative example 8 was essentially the same as that of corn crude oil of example 1 except that the retention time in the deodorizing tower 1 used in comparative example 8 was different, and according to the analysis of the result, when the corn crude oil contains gibberellin at 5800mg/kg, the temperature of the tower 1 was used: 240 ℃; time: 60 minutes; vacuum (residual pressure): 250 Pa; the direct steam pressure is 0.03Mpa under the process conditions:
The zearalenone in comparative example 8 was reduced to 113ug/kg, which is 67ug/kg less than that in example 1;
the 3-chloropropanol ester and the glycidyl ester in the comparative example 8 are 1295ug/kg and 1098ug/kg respectively, which are respectively increased compared with the example 1, 380ug/kg and 268ug/kg are respectively increased, and the limits of 1250ug/kg and 1000ug/kg of the enterprise industry control standard limit are respectively exceeded;
the trans fatty acid content in comparative example 8 was 1.65%, and the increase was greater than the trans fatty acid content of 1.20% in example 1 by 0.45%;
the VE content in comparative example 8 was 11.2mg/100g, which was a larger reduction in the amount of 10.3mg/100g than that in example 1;
the phytosterol content in comparative example 8 was 4345ug/kg, which was a greater reduction than the phytosterol content in example 1, which was 2505ug/kg.
The corn oil has longer residence time in the deodorization tower 1 when the content of the zearalenone in the crude oil is higher, and the content of the zearalenone is reduced when the decomposition of harmful components in the processing process is more; however, the production of harmful components trans fatty acid, 3-chloropropanol ester and glycidyl ester is greatly increased; meanwhile, the longer the deodorization residence time is, the more the retention of the beneficial component VE and the plant sterol is reduced; the temperature has little effect on the acid value.
Comparative example 9:
the raw materials and the process of this comparative example were substantially the same as in example 2, except that the residence time in the deodorizing tower 1 was 30 minutes.
Table 9 data statistics table for comparative example 9 and example 2
The procedure for the production of corn oil of comparative example 9 was substantially the same as that of corn crude oil of example 2 except that the retention time in the deodorizing tower 1 used in comparative example 9 was different, and according to the analysis of the result, when the corn crude oil contains 4600mg/kg of gibberellin, the temperature of the tower 1 was used: 235 ℃; time: 30 minutes; vacuum (residual pressure): 250 Pa; the direct steam pressure is 0.03Mpa under the process conditions:
the content of zearalenone in comparative example 9 is increased to 283ug/kg, which is obviously greater than that in example 2 by 158 ug/kg;
the 3-chloropropanol ester and the glycidyl ester in comparative example 9 were 635ug/kg and 605ug/kg, respectively, which were reduced by 350ug/kg and 273ug/kg, respectively, as compared with example 2;
the trans fatty acid content in comparative example 9 was 0.56%, and the reduction was not large, compared with the trans fatty acid content of 0.70% in example 2, and was reduced by 0.14%;
the VE content in comparative example 9 was 29.8mg/100g, which was increased by 6.8mg/100g as compared to the VE content in example 2;
The phytosterol content in comparative example 9 was 8365ug/kg, which was increased by a larger margin than that in example 2, by 1350ug/kg.
The method shows that when the content of the zearalenone in crude oil is moderate, the shorter the retention time of the corn oil in a deodorization tower is, the decomposition of the zearalenone which is a harmful component in the processing process is reduced, and the content increase range is obvious; the reduction amount of the harmful component trans fatty acid is limited; but the production amount of the harmful components of 3-chloropropanol ester and glycidyl ester is obviously reduced; meanwhile, the shorter the deodorization residence time is, the more obvious the retention amount of the beneficial component VE and the plant sterol is increased; the temperature has little effect on the acid value.
Comparative example 10:
the raw materials and the process of this comparative example were substantially the same as in example 2, except that the residence time in the deodorizing tower 1 was 50 minutes.
Table 10 comparative example 10 and example 2 data statistics table
The procedure for the production of corn oil of comparative example 10 was substantially the same as that of corn crude oil of example 2 except that the retention time in the deodorizing tower 1 used in comparative example 10 was different, and according to the analysis of the result, when the corn crude oil contains 4600mg/kg of gibberellin, the temperature of the tower 1 was used: 235 ℃; time: 50 minutes; vacuum (residual pressure): 250 Pa; the direct steam pressure is 0.03Mpa under the process conditions:
The zearalenone in comparative example 10 is reduced to 75ug/kg, which is reduced by 50ug/kg compared with the zearalenone in example 2, and the reduction is obvious;
the 3-chloropropanol ester and the glycidyl ester in comparative example 10 were 1385ug/kg and 1255ug/kg, respectively, which were increased by 400ug/kg and 377ug/kg, respectively, as compared with example 2;
the trans fatty acid content in comparative example 10 was 1.55%, and the increase was greater than 0.70% in example 2 by 0.85%;
the VE content in comparative example 10 was 18.8mg/100g, which was a larger reduction in the amount of 4.2mg/100g than that in example 2;
the plant sterol content in comparative example 10 was 3235ug/kg, and the reduction was large compared with the plant sterol content in example 2, and 3780ug/kg was reduced.
The method shows that when the content of the zearalenone in crude oil is moderate, the longer the corn oil stays in the deodorization tower, the decomposition of the harmful component zearalenone in the processing process is increased, and the content is reduced; the increase of the harmful component trans fatty acid is obvious; however, the production of 3-chloropropanol ester and glycidyl ester which are harmful components is greatly increased; meanwhile, the longer the deodorization residence time is, the more obviously the retention of the beneficial component VE and the plant sterol is reduced; the temperature has little effect on the acid value.
Comparative example 11:
the raw materials and the process of this comparative example were substantially the same as in example 3, except that the residence time in the deodorizing tower 1 was 20 minutes.
Table 11 comparative example 11 and example 3 data statistics table
The procedure for the production of corn oil of comparative example 11 was essentially the same as that of corn crude oil of example 3 except that the retention time in the deodorizing tower 1 used in comparative example 11 was different, and according to the analysis of the result, when the corn crude oil contains gibberellin at 1700mg/kg, the temperature of the tower 1 was used: 230 ℃; time: 20 minutes; vacuum (residual pressure): 250 Pa; the direct steam pressure is 0.03Mpa under the process conditions:
the content of zearalenone in comparative example 11 is increased to 155ug/kg, which is obviously increased compared with that in example 3 by 70 ug/kg;
the 3-chloropropanol ester and the glycidyl ester in comparative example 11 were 245ug/kg and 163ug/kg, respectively, which were reduced by 180ug/kg and 193ug/kg, respectively, as compared with example 3;
the trans fatty acid content in comparative example 11 was 0.36%, and the reduction was significantly reduced by 0.24% as compared with the trans fatty acid content of 0.60% in example 3;
the VE content in comparative example 11 was 32.0mg/100g, which was significantly increased by 4.0mg/100g as compared to the VE content of 28.0mg/100g in example 2;
The phytosterol content in comparative example 11 was 8995ug/kg, which was slightly increased compared to the phytosterol content in example 2, with insignificant amplitude.
The lower the content of the zearalenone in crude oil is, the shorter the retention time of the corn oil in the deodorization tower 1 is, the less the decomposition of the harmful component zearalenone in the processing process is, and the content is increased; the reduction of the trans fatty acid of the harmful component is obvious; however, the production amount of the harmful components of 3-chloropropanol ester and glycidyl ester is greatly reduced; meanwhile, the shorter the deodorization residence time is, the more obvious the beneficial component VE is retained, and the less obvious the retention amount of the phytosterol is increased; the temperature has little effect on the acid value.
Comparative example 12:
the raw materials and the process of this comparative example were substantially the same as in example 3, except that the residence time in the deodorizing tower 1 was 40 minutes.
Table 12 comparative example 12 and example 3 data statistics table
The procedure for the production of corn oil of comparative example 12 was essentially the same as that of corn crude oil of example 3 except that the retention time in the deodorizing tower 1 used in comparative example 12 was different, and according to the analysis of the result, when the corn crude oil contains gibberellin at 1700mg/kg, the temperature of the tower 1 was used: 230 ℃; time: 40 minutes; vacuum (residual pressure): 250 Pa; the direct steam pressure is 0.03Mpa under the process conditions:
The reduction of zearalenone in comparative example 12 to 53ug/kg was less pronounced than the 32ug/kg reduction of zearalenone in example 3;
the 3-chloropropanol ester and the glycidyl ester in comparative example 12 were 867ug/kg and 735ug/kg, respectively, which were increased compared to example 3 by 442ug/kg and 379ug/kg, respectively;
the trans fatty acid content in comparative example 12 was 0.88%, and the increase was significantly increased by 0.28% as compared with the trans fatty acid content of 0.60% in example 3;
the VE content in comparative example 12 was 21.6mg/100g, which was significantly reduced by 6.4mg/100g as compared to the VE content of 28.0mg/100g in example 3;
the phytosterol content in comparative example 12 was 5605ug/kg, a significant reduction was seen, 3390ug/kg was reduced, as compared to 8995ug/kg in example 3.
The corn gibberellin is decomposed and increased in the processing process when the corn oil stays in the deodorizing tower 1 for a longer time when the corn gibberellin content in crude oil is smaller, and the content reduction range is limited; the increase of the harmful component trans fatty acid is obvious; however, the production of 3-chloropropanol ester and glycidyl ester which are harmful components is greatly increased; meanwhile, the longer the deodorization residence time is, the less the retention of the beneficial component VE is affected obviously, and the less the retention of the phytosterol is affected obviously; the temperature has little effect on the acid value.
The detection methods of the corn oil obtained in the above examples and comparative examples are determined according to the corn oil national standard (GB/T19111-2017) and the enterprise internal control restriction index: the zearalenone is judged according to the enterprise internal control standard, and the content is less than or equal to 300ug/kg; the alpha-VE equivalent is judged according to the enterprise internal control standard, and is more than or equal to 21mg/100g; the trans-fatty acid content is judged according to the enterprise internal control standard, and is less than or equal to 2%; the 3-chloropropanol ester content is judged according to the enterprise internal control standard, and is less than or equal to 1250ug/kg (refer to European Union standard); the glycidyl ester is judged according to the enterprise internal control standard, and the glycidyl ester is less than or equal to 1000ug/kg (refer to European Union standard); the rest are judged according to national standards.
Through the single factor analysis of the process conditions, the beneficial components of plant sterols and VE in the corn oil are maintained, and the contents of harmful substances of zearalenone, trans-fatty acid, 3-chloropropanol ester and water-locking glyceride in the corn oil are reduced, so that the balance among indexes is achieved, and the corn oil has great technical difficulty. The invention carries out the grading control of the process according to the different contents of the corn crude oil and the corn gibberellin, particularly carries out the grading strict control of the process conditions in the decoloring stage and the process stage of the deodorization tower 1, and the close matching of the process steps solves the contradiction point that the other corresponding indexes are negatively influenced only for one or a plurality of corn oil indexes in the prior art, realizes the purpose of keeping the beneficial components in the corn oil and simultaneously reduces the contents of harmful components in the corn oil and ensures that the components reach good balance points.
Claims (5)
1. A corn oil moderate processing technology is characterized by comprising the following steps:
(1) Degumming: heating corn crude oil to 60 ℃, adding 85% food grade phosphoric acid, wherein the dosage of the food grade phosphoric acid is 0.05% of that of the corn crude oil, performing acid treatment, and then washing the crude oil by adopting chlorine-free soft water;
(2) Alkali refining deacidification: the degummed corn oil reacts with liquid alkali, and then the corn oil is washed by adopting chlorine-free soft water until the residual soap in the corn oil is less than 300mg/kg; the concentration of the liquid alkali is 16 Baume degrees, and the super alkali amount is 20%;
(3) Decoloring: the deacidified corn oil is pumped into a decoloring tower for decoloring, the dosage of a decoloring agent is 0.5-5% of that of the corn oil, the decoloring agent is a mixture of activated clay and plant activated carbon, wherein the addition of the plant activated carbon accounts for 10-20% of that of the activated clay, the decoloring temperature is 110-120 ℃, and the decoloring time is controlled so that the content of zearalenone in the decolored corn oil is controlled within the following range:
when the content of zearalenone in the crude maize oil is more than 5000ug/kg, controlling the content of zearalenone in the decolored maize oil to be not higher than 1500ug/kg;
when the content of zearalenone in the crude corn oil is 3000-5000ug/kg, controlling the content of zearalenone in the decolorized corn oil to be not higher than 1000ug/kg;
When the content of zearalenone in crude corn oil is less than 3000ug/kg, controlling the content of zearalenone in decolorized corn oil to be not higher than 800ug/kg;
(4) Dewaxing: pumping the decoloration oil into a gradient cooling multistage crystallization tank, and growing crystals, wherein the cooling rate in the gradient cooling process is as follows: the temperature is reduced to 15 ℃ at 30 ℃ for 4 hours; the temperature is reduced to 10 ℃ at 15 ℃ for 4 hours; the temperature is reduced to 5 ℃ from 10 ℃ and the time is 3 hours; raising the temperature to 7 ℃ at 5 ℃ for 1 hour; separating dewaxed corn oil;
(5) Deodorizing: the double-tower process is adopted, and the concrete steps are as follows:
the deodorization tower 1 is a laminate tower, and the process conditions in the deodorization tower 1 are controlled as follows:
when the corn crude oil gibberellin ketone is more than 5000ug/kg, the temperature of the deodorization tower 1 is controlled at 240 ℃, the retention time is controlled at 50 minutes, and the direct steam pressure is 0.03Mpa;
when corn crude oil gibberellin ketone is 3000-5000ug/kg, the temperature of the deodorization tower 1 is controlled at 235 ℃, the retention time is controlled at 40 minutes, and the direct steam pressure is 0.03Mpa;
when the corn crude oil gibberellin ketone is less than 3000ug/kg, the temperature of the deodorization tower 1 is controlled at 230 ℃, the retention time is controlled at 30 minutes, and the direct steam pressure is 0.03Mpa;
the deodorization tower 2 is a falling film tower, the deodorization temperature is controlled to be 190-220 ℃, and the retention time is controlled to be 30 minutes;
(6) Refining post-treatment: and (3) re-adsorbing the deodorized corn oil by adopting an adsorbent under the pressure of less than 1Mbar and the temperature of 120 ℃, wherein the adsorbent adopts diatomite, and the using amount of the adsorbent is 0.2% -0.5% of the corn oil.
2. The corn oil moderate-processing process of claim 1, wherein the storage temperature of the raw corn germ from which the corn crude oil is produced is not higher than 30 ℃.
3. The corn oil moderate-processing process according to claim 1, wherein the drying treatment of the raw corn germ for producing the corn crude oil is: drying the corn germ at a temperature below 130 ℃ until the moisture content is below 9%.
4. The moderate-processing process of corn oil according to claim 1, wherein a filter aid diatomaceous earth is added to the dehydrated oil before pumping into the gradient cooled multistage crystallization tank.
5. The moderate-processing process of corn oil according to claim 1, wherein the dewaxing step of step (4) is performed at an ambient temperature of 18 to 25 ℃.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017070240A1 (en) * | 2015-10-23 | 2017-04-27 | NanoGuard Technologies, LLC | Reactive gas generation system and method of treatment using reactive gas |
| CN108611188A (en) * | 2016-12-09 | 2018-10-02 | 丰益(上海)生物技术研发中心有限公司 | A kind of grease processing technique |
| CN108707508A (en) * | 2018-06-29 | 2018-10-26 | 山东三星玉米产业科技有限公司 | Corn degumming of oil dewaxing one-step method refinery practice |
| CN109536275A (en) * | 2019-01-28 | 2019-03-29 | 武汉轻工大学 | A kind of method that appropriateness processing prepares peanut oil |
| CN109609264A (en) * | 2019-02-15 | 2019-04-12 | 佳乐宝食品股份有限公司 | A kind of refinery practice improving corn oil quality |
| CN113773906A (en) * | 2021-09-29 | 2021-12-10 | 山东三星玉米产业科技有限公司 | Safe, nutritional, energy-saving and low-consumption corn oil production process |
| CN115058287A (en) * | 2022-05-13 | 2022-09-16 | 山东三星玉米产业科技有限公司 | Zero-trans-fatty-acid low-toxin corn oil refining process |
| CN115873658A (en) * | 2022-12-22 | 2023-03-31 | 长寿花食品股份有限公司 | Process for removing zearalenone toxin from corn germ in vegetable oil |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116948743A (en) * | 2023-07-21 | 2023-10-27 | 长寿花食品股份有限公司 | Control method of trichloropropanol ester and glycidyl ester in corn oil deodorization working section |
-
2023
- 2023-09-20 CN CN202311212543.5A patent/CN116948744B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017070240A1 (en) * | 2015-10-23 | 2017-04-27 | NanoGuard Technologies, LLC | Reactive gas generation system and method of treatment using reactive gas |
| CN108611188A (en) * | 2016-12-09 | 2018-10-02 | 丰益(上海)生物技术研发中心有限公司 | A kind of grease processing technique |
| CN108707508A (en) * | 2018-06-29 | 2018-10-26 | 山东三星玉米产业科技有限公司 | Corn degumming of oil dewaxing one-step method refinery practice |
| CN109536275A (en) * | 2019-01-28 | 2019-03-29 | 武汉轻工大学 | A kind of method that appropriateness processing prepares peanut oil |
| CN109609264A (en) * | 2019-02-15 | 2019-04-12 | 佳乐宝食品股份有限公司 | A kind of refinery practice improving corn oil quality |
| CN113773906A (en) * | 2021-09-29 | 2021-12-10 | 山东三星玉米产业科技有限公司 | Safe, nutritional, energy-saving and low-consumption corn oil production process |
| CN115058287A (en) * | 2022-05-13 | 2022-09-16 | 山东三星玉米产业科技有限公司 | Zero-trans-fatty-acid low-toxin corn oil refining process |
| CN115873658A (en) * | 2022-12-22 | 2023-03-31 | 长寿花食品股份有限公司 | Process for removing zearalenone toxin from corn germ in vegetable oil |
Non-Patent Citations (2)
| Title |
|---|
| 吸附法脱除玉米油中玉米赤霉烯酮的研究;刘玉兰等;《粮油与油脂》;第29卷(第9期);第6-10页 * |
| 精炼加工对玉米油营养指标和风险指标的影响;尚刚等;《中国油脂》(第02期);第22-27页 * |
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