CN110938490A - Method for reducing content of 3-chloropropanol ester, 2-chloropropanol ester and glycidyl ester in edible oil - Google Patents
Method for reducing content of 3-chloropropanol ester, 2-chloropropanol ester and glycidyl ester in edible oil Download PDFInfo
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- CN110938490A CN110938490A CN201811114163.7A CN201811114163A CN110938490A CN 110938490 A CN110938490 A CN 110938490A CN 201811114163 A CN201811114163 A CN 201811114163A CN 110938490 A CN110938490 A CN 110938490A
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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
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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
- C11B3/12—Refining fats or fatty oils by distillation
Abstract
The invention relates to a method for reducing the content of 3-MCPD ester, 2-MCPD ester and glycidyl ester in edible oil, which comprises the following steps: heating the initial grease to 60-90 ℃, feeding the initial grease into a film evaporator at a feeding rate of 300-700 kg/h for evaporation to obtain grease A, wherein the temperature of the film evaporator is 120-180 ℃; then, the grease A enters a rotary wiped film type molecular distiller for molecular distillation, so that light components and heavy components are obtained; and cooling and collecting the obtained light components, and cooling and directly collecting the heavy components as an oil product, wherein the temperature of an evaporation surface of the rotary wiped film type molecular distiller is 190-270 ℃, the wiped film rate is 60-300 r/min, and the vacuum degree is 0.1-100 Pa. The method further reduces the content of 3-MCPD ester, 2-MCPD ester and glycidyl ester in the initial oil (such as refined edible oil), is more suitable for application of oil processing enterprises, and can produce healthier edible oil.
Description
Technical Field
The invention relates to the technical field of oil processing, in particular to a method for reducing the content of 3-chloropropanol ester, 2-chloropropanol ester and glycidyl ester in edible oil.
Background
Chloropropanol esters and glycidyl esters are edible oil hazards that have attracted considerable attention in recent years. The chloropropanol ester is formed by esterifying chloropropanol compound with fatty acid, wherein the highest content is 3-chloropropanol ester (3-MCPD ester) and 2-chloropropanol ester (2-MCPD ester). The content of chloropropanol ester in the grease is far higher than that of free chloropropanol. Currently, the safety of chloropropanol ester is unknown, and there is no direct evidence that it has a negative effect on human health. However, studies have shown that 3-MCPD ester releases free 3-chloropropanol under the action of intestinal pancreatic lipase, and that 3-chloropropanol is a class 2B carcinogen assessed by the International cancer organization. The German Federal Risk assessment organization (BfR) and the European Food Safety Administration (EFSA) agree that a risk assessment should be made for 3-MCPD esters based on toxicological data of 3-chloropropanol, i.e. 3-MCPD esters are completely hydrolysed in the gastrointestinal tract to 3-chloropropanol and 3-chloropropanol is one hundred percent derived from 3-MCPD esters. 2-MCPD ester has not enough toxicological data at present, but is a substance of great concern to enterprises and consumers.
Glycidyl esters are the esterification products of glycidyl oil and fatty acids. In 2008, BfR demonstrated for the first time the ubiquitous presence of glycidyl esters in refined edible oils. Also, glycidyl esters are readily converted to 3-MCPD esters in the presence of chloride ions. Glycidyl ester does not have carcinogenicity per se, but glycidyl produced by metabolism in the digestive tract has gene carcinogenicity, and the glycidyl ester is evaluated as a grade 2A carcinogen by the international cancer organization.
The content level of chloropropanol compounds in 491 batches of edible vegetable oil samples of 10 vegetable oil varieties is tested by Wuhan food cosmetic inspection institute in China, and the result shows that the detection rate of 3-MCPD ester is 83.3%, and the detection result range is 0.104ppm-8.580 ppm. Wherein, the oil with higher 3-MCPD ester content is palm oil and camellia seed oil, then corn oil, peanut oil and sesame oil, and the oil with lower 3-MCPD ester content is olive oil and soybean oil.
It is known that 3-MCPD esters, 2-MCPD esters and glycidyl esters are mainly produced in the deodorization section in the refining of fats and oils. Thus, the prior art generally reduces the production of 3-MCPD esters, 2-MCPD esters and glycidyl esters by controlling and optimizing the processes of deodorization, etc. during refining. For example, patent application CN 106281672 a discloses a method for reducing 3-MCPD esters in fats and oils by contacting the fats and oils with antioxidants and/or antioxidant derivatives; patent application CN 10494250A discloses a method for reducing 3-MCPD esters and/or glycidyl esters in fats and oils by adding one or more antioxidants to the fats and oils after decolorization or before deodorization, followed by deodorization. Both of these methods involve adding a large amount of antioxidant to the oil and fat, which inevitably results in residual antioxidant and a significant increase in production cost. Patent application CN 104531349 a discloses a method for reducing the content of 3-MCPD ester in grease by reducing the content of iron ions, but does not disclose data of iron ions in grease in actual industrial production and specific values of the content of 3-MCPD ester in grease after treatment. Patent CN 103525550B discloses a deodorization method for reducing the content of 3-MCPD ester in vegetable oil, but the content of 3-MCPD ester in the oil treated by the method is 70ppm at the lowest, and still high.
Therefore, the existing patent mainly starts from the crude oil end, and reduces the generation of 3-MCPD ester by changing and optimizing the process conditions of the refining process of the oil; for glycidyl ester, the content of glycidyl ester is mostly reduced by additionally adding adsorbent treatment. Because the prior art mainly focuses on optimizing the process conditions in the oil refining process, the process is complex and the practicability is poor, and the current control technologies related to 3-MCPD ester, 2-MCPD ester and glycidyl ester are not widely popularized to most oil processing enterprises.
The contents of 3-MCPD ester, 2-MCPD ester and glycidyl ester in a plurality of grease products at home and abroad are all at a higher level, and the grease product has potential threat to the health of consumers. However, there is currently a lack of effective methods for further removing the high levels of 3-MCPD esters, 2-MCPD esters, and glycidyl ester systems present in the market for many of the refined grease products.
Therefore, in the field of oil and fat processing, a method capable of further reducing the content of 3-chloropropanol ester, 2-chloropropanol ester and glycidyl ester in edible oil and fat is urgently needed, so that the method is suitable for application of oil and fat processing enterprises, and healthier edible oil and fat can be simply and efficiently produced.
Disclosure of Invention
The inventor researches and discovers that when the rotary wiped film type molecular distiller is used for distilling the grease product, different process conditions such as temperature, vacuum degree and the like have significant influence on the content of 3-MCPD ester, 2-MCPD ester and glycidyl ester in the final grease product. The invention can simultaneously reduce the contents of the three substances of 3-MCPD ester, 2-MCPD ester and glycidyl ester in the edible oil and fat by utilizing the rotary wiped film type molecular distiller and combining optimized process conditions, and reduce the contents of the 3-MCPD ester, the 2-MCPD ester and the glycidyl ester to less than 1.0ppm, preferably less than 0.5ppm, and further preferably less than 0.3 ppm. The method disclosed by the invention is simple to operate, strong in practicability and more suitable for application of grease processing enterprises.
The above purpose of the invention is realized by the following technical scheme:
the invention provides a method for reducing the content of 3-MCPD ester, 2-MCPD ester and glycidyl ester in edible oil, which comprises the following steps:
heating initial grease to 60-90 ℃, and then feeding the initial grease into a thin film evaporator at a feeding rate of 300-700 kg/h to remove low boiling point substances such as water, residual solvent and the like, so as to obtain grease A, wherein the temperature of the thin film evaporator is 120-180 ℃; the method comprises the steps of enabling oil A to directly enter a rotary wiped film type molecular distiller for molecular distillation to obtain a light component and a heavy component, enabling the light component to be cooled and collected, and enabling the heavy component to be cooled and directly collected to serve as an oil product, wherein the evaporation surface temperature of the rotary wiped film type molecular distiller is 190-270 ℃, the wiped film rate is 60-300 r/min, and the vacuum degree is 0.1-100 Pa.
Specifically, the invention is realized by the following technical scheme:
[1] a method of reducing the content of 3-MCPD esters, 2-MCPD esters, and glycidyl esters in an edible oil or fat, the method comprising:
heating the initial grease to 60-90 ℃, feeding the initial grease into a film evaporator at a feeding rate of 300-700 kg/h for evaporation to obtain grease A, wherein the temperature of the film evaporator is 120-180 ℃;
and (2) allowing the grease A to enter a rotary wiped film type molecular distiller for molecular distillation to obtain a light component and a heavy component, wherein the heavy component is a grease product, the temperature of an evaporation surface of the rotary wiped film type molecular distiller is 190-270 ℃, the wiped film rate is 60-300 r/min, and the vacuum degree is 0.1-100 Pa.
[2] The method of paragraph [1], wherein the starting grease is warmed to 70 ℃ to 85 ℃.
[3] The method of any of paragraphs [1] or [2], wherein the feed rate is from 300kg/h to 500 kg/h.
[4] The process as described in any of paragraphs [1] to [3], wherein the temperature of the thin film evaporator is from 130 ℃ to 150 ℃.
[5] The process as described in any of paragraphs [1] to [4], wherein the evaporation surface of the rotary wiped film molecular still has a temperature of from 210 ℃ to 270 ℃.
[6] The method of any of paragraphs [5], wherein the evaporation surface of the rotary wiped film molecular still has a temperature of 230 ℃ to 240 ℃.
[7] The method according to any one of paragraphs [1] to [6], wherein the film-scraping rate is from 100r/min to 200 r/min.
[8] The process according to any one of paragraphs [1] to [7], wherein the vacuum degree is from 0.5Pa to 50 Pa.
[9] The method of any of paragraphs [1] to [8], wherein the starting oil is a refined vegetable or animal oil selected from one or more of the group consisting of: corn oil, sunflower oil, palm oil, soybean oil, rice oil, palm olein, palm stearin, palm oil medium melting point fraction, palm olein, palm kernel oil, coconut oil, rapeseed oil, cottonseed oil, safflower oil, high oleic sunflower oil, high oleic soybean oil, hazelnut oil, tea seed oil, olive oil, wheat germ oil, sesame oil, algae oil, grape seed oil, safflower oil, perilla seed oil, beef tallow, lard, chicken oil, butter, fish oil, whale oil and mutton fat, and modified fats obtained by extremely hydrogenating and fractionating these fats.
[10] The process as described in any one of paragraphs [1] to [9], wherein the temperature of the starting grease is raised by passing the starting grease through a heat exchanger.
[11] The process according to any one of paragraphs [1] to [10], wherein the moisture content of the fat A is 0.2 wt% or less.
[12] The method according to paragraph [11], wherein the moisture content of the fat A is 0.15 wt% or less.
[13] The method according to any one of paragraphs [1] to [12], wherein the content of n-hexane in the fat A is 20mg/kg or less.
[14] The method according to paragraph [13], wherein the oil A has a n-hexane content of 15mg/kg or less.
[15] The process as described in any one of paragraphs [1] to [14], wherein the heavy component is cooled to below 60 ℃ and collected, and the heavy component is cooled by a heat exchanger.
[16] The process as described in any one of paragraphs [1] to [15], wherein the temperature of the light component is reduced by an internal condenser of the rotary wiped film molecular still, and the condensing surface temperature of the internal condenser is 40 ℃ to 70 ℃.
[17] The method according to any one of paragraphs [1] to [16], wherein the content of 3-MCPD ester, 2-MCPD ester and glycidyl ester in the grease product is 1.0ppm or less.
[18] The method according to paragraph [17], wherein the content of the 3-MCPD ester, the 2-MCPD ester and the glycidyl ester in the oil or fat product is 0.5ppm or less.
[19] The method as described in paragraph [18], wherein the content of 3-MCPD ester, 2-MCPD ester and glycidyl ester in the grease product is 0.3ppm or less.
Detailed Description
The following examples further illustrate specific embodiments of the present invention in detail, but the scope of the present invention is not limited thereto.
In the present invention, the "starting fats and oils" used are refined vegetable or animal oils including, but not limited to, the following vegetable or animal oils: corn oil, sunflower seed oil, palm oil, soybean oil, rice oil, palm olein, palm stearin, palm oil medium melting point fraction, palm olein, palm kernel oil, coconut oil, rapeseed oil, cottonseed oil, safflower seed oil, high oleic sunflower oil, high oleic soybean oil, hazelnut oil, tea seed oil, olive oil, wheat germ oil, sesame oil, algae oil, grape seed oil, safflower oil, perilla seed oil, beef tallow, lard, chicken oil, butter, fish oil, whale oil, sheep oil, and modified oils obtained by extremely hydrogenating and fractionating these oils.
In the present invention, the "refining" means subjecting the vegetable oil or the animal oil to one or more treatment steps of degumming, deacidification, decoloration, deodorization, dewaxing, etc.
In the present invention, the term "high oleic acid" refers to oleic acid having an oleic acid content of 60% or more relative to the total amount of fatty acids in the fat or oil.
In the present invention, the term "extremely hydrogenated" means that unsaturated fatty acids in fats and oils are converted into saturated fatty acids by hydrogenation treatment so that iodine value of the fats and oils is less than 4g I2/100g。
In the invention, the fractionation is based on a thermodynamic fully reversible physical modification method, high-melting-point components are crystallized by cooling according to the difference of melting points of different components in the grease, and the components with different melting points and different purposes are obtained by filtration or centrifugal separation.
In one aspect of the present invention, the present invention provides a method for reducing the content of 3-MCPD esters, 2-MCPD esters and glycidyl esters in an edible fat or oil, the method comprising:
heating the initial grease to 60-90 ℃, feeding the initial grease into a thin film evaporator at a feeding rate of 300kg/h-700kg/h, preferably at a feeding rate of 300kg/h-500kg/h, and evaporating to obtain grease A, wherein the temperature of the thin film evaporator is 120-180 ℃, preferably 130-150 ℃;
and (2) directly feeding the grease A into a rotary wiped film type molecular distiller for molecular distillation to obtain light components and heavy components, wherein the heavy components are grease products, the temperature of an evaporation surface of the rotary wiped film type molecular distiller is 190-270 ℃, preferably 210-270 ℃, further preferably 230-240 ℃, the wiped film rate is 60-300 r/min, preferably 100-200 r/min, and the vacuum degree is 0.1-100 Pa, preferably 0.5-50 Pa.
In one embodiment, the starting grease is warmed to 70 ℃ to 85 ℃ by a heat exchanger.
In the present invention, "heat exchanger" includes, but is not limited to, one or more selected from the group consisting of: dividing wall heat exchangers, such as tube heat exchangers, plate heat exchangers, fin heat exchangers; hybrid heat exchangers and regenerative heat exchangers.
The thin film evaporation process is based on a simple distillation principle. In a thin-film evaporator, the medium to be evaporated or the solution to be concentrated is applied as a thin film to the evaporation zone, whereby a short contact with the heating zone takes place. Thus, it is possible to use thermally unstable media or substances, and in particular under vacuum or reduced pressure, which will experience very short evaporation times. Many different types of thin film evaporators known in the art can be used, such as climbing film, falling film, and wiped film evaporators.
In the invention, the thin film evaporator is mainly used for removing low boiling point substances such as water, residual solvent and the like in the initial grease, thereby avoiding the bumping phenomenon in the subsequent molecular distiller and the adverse effect on a vacuum pump. Wherein the residual solvent comprises n-hexane, isohexane, isopropanol, ethanol, etc. Thus, any type of thin film evaporator commonly used in the art may be used in the present invention. In a preferred embodiment, the thin film evaporator may use an LFE-600 type thin film evaporator.
In a preferred embodiment, the temperature of the thin film evaporator may be from 120 ℃ to 180 ℃, preferably from 130 ℃ to 150 ℃.
The moisture content of the fat or oil A obtained by the thin film evaporator is 0.2 wt% or less, for example, 0.15 wt% or less, 0.1 wt% or less, 0.05 wt% or less, 0.01 wt% or less, 0.005 wt% or less, or 0 (undetectable, i.e., below the detection limit).
As an example, the fat A obtained by the thin film evaporator has an n-hexane solvent content of 20mg/kg or less, for example, 15mg/kg or less, 10mg/kg or less, 5mg/kg or less, or 0 (undetectable, i.e., below the detection limit). In the present invention, as for the content of the residual solvent, the content of n-hexane is preferably used as an indicator.
In a particular embodiment of the invention, the feed rate is from 300kg/h to 700kg/h, preferably from 300kg/h to 500 kg/h. If the feeding speed is too slow, the productivity is reduced and the energy consumption of equipment is increased; if the feed rate is too fast, the feed liquid cannot be distributed efficiently on the evaporation surface, resulting in increased liquid film thickness and reduced removal efficiency of 3-MCPD esters, 2-MCPD esters, and glycidyl esters.
The molecular distillation has low operation temperature, high vacuum degree, short heating time, high separation efficiency and the like, and is particularly suitable for separating high-boiling point, heat-sensitive and easily-oxidized substances. The wiped film type molecular distiller becomes the mainstream molecular distiller at present due to simple structure and low equipment operation cost. The wiped film type molecular distiller is an effective improvement on the traditional falling film type molecular distiller, and a rotating wiped film device is arranged in the falling film type molecular distiller to scrape liquid into a liquid film with uniform thickness on an evaporation surface.
In the present invention, a rotary wiped film type molecular still is preferably used.
In the present invention, the thin film evaporator and the rotary wiped film molecular still are connected by a pipeline, preferably a stainless steel pipeline.
For the sake of saving time and energy, the fat A obtained via the thin film evaporator is passed directly into the rotary wiped film molecular still via the connecting line of the thin film evaporator and the rotary wiped film molecular still.
In a specific embodiment of the present invention, the temperature of the evaporation surface of the molecular still is controlled to 190 ℃ to 270 ℃, preferably 210 ℃ to 270 ℃, and more preferably 230 ℃ to 240 ℃. If the temperature of the evaporation surface is too high, the content of 3-MCPD ester, 2-MCPD ester and glycidyl ester is increased; if the temperature of the evaporation surface is too low, the evaporation rate decreases, and the removal effect of the 3-MCPD ester, 2-MCPD ester, and glycidyl ester becomes poor.
In a specific embodiment of the invention, the film scraping rate of the molecular still is controlled to be 60r/min-300r/min, preferably 100r/min-200 r/min. If the film scraping speed is too fast, the energy consumption of the system is increased; if the film scraping speed is too slow, the materials cannot be uniformly distributed on the surface of the evaporator, the thickness of a liquid film is increased, and the removal efficiency of the 3-MCPD ester, the 2-MCPD ester and the glycidyl ester is reduced.
In a particular embodiment of the invention, the degree of vacuum of the distillation system is between 0.1Pa and 100Pa, preferably between 0.5Pa and 50 Pa. If the vacuum degree is too high, the energy consumption of the system is increased; if the degree of vacuum is too low, the removal efficiency of the 3-MCPD ester, 2-MCPD ester and glycidyl ester decreases.
In the present invention, the term "light component" is used to mean a substance which escapes from the liquid surface to the surface of the condenser for molecular distillation and is condensed and discharged, while the liquid mixture is flowing along the evaporation surface and heated. In the present invention, the "light component" mainly comprises 3-MCPD ester, 2-MCPD ester, glycidyl ester, free fatty acid, monoglyceride and diglyceride.
As used herein, "heavy components" refers to materials that escape the liquid surface but fail to reach the condenser surface and are thus discharged along the mixed liquor as the liquid mixture flows along the evaporation surface and is heated. In the present invention, the "heavy component" is mainly triglyceride in the edible oil and fat. For example, in embodiments where refined corn oil is the starting oil, the heavy component comprises primarily triglycerides contained in the corn oil.
In some embodiments, the 3-MCPD ester, 2-MCPD ester and glycidyl ester content in the grease product is reduced to below 1.0ppm, preferably below 0.5ppm, further preferably below 0.3ppm according to the process of the present invention.
In a further preferred embodiment, the light fraction is cooled to below 70 ℃ and collected; and cooling the heavy component to below 60 ℃ and collecting. The light fraction is usually collected in a light fraction collection tank provided with the rotary wiped film molecular still, and the heavy fraction is collected in a heavy fraction collection tank provided with the rotary wiped film molecular still.
In a specific embodiment of the invention, the temperature of the light fraction is reduced by means of a built-in condenser of the rotary wiped film molecular still. In one embodiment, the condensing surface temperature of the built-in condenser is 40 ℃ to 70 ℃. In the present invention, after the light component is cooled by the built-in condenser, the temperature of the obtained light component is substantially equal to the temperature of the built-in condenser.
In one embodiment of the invention, the heavy fraction is cooled by means of a heat exchanger provided in the rotary wiped-film molecular still. The detection method of 3-MCPD ester, 2-MCPD ester and glycidyl ester in edible oil is determined by referring to AOCS Cd29a-13 method, namely, firstly, glycidyl ester is converted into 3-bromopropylene glycol (3-MBPD) monoester in acid solution of bromide salt, then the 3-MBPD ester, the 3-MCPD ester and the 2-MCPD ester are converted into free form in acid methanol solution, and then the free form is subjected to GC-MS analysis after derivation by phenylboronic acid.
Examples
The present invention will be described in further detail with reference to examples. These examples are merely illustrative and should not be construed as limiting the scope of the invention. All technical solutions and modifications thereof implemented based on the above contents of the present invention fall within the scope of the present invention.
The refined oils used in the following examples were obtained from samples taken from commercial or domestic grease processing plants.
For each starting grease, the contents of 3-MCPD ester, 2-MCPD ester and glycidyl ester therein were determined according to AOCS Cd29a-13 method by:
(1) acid hydrolysis
100 + -5 mg of sample was weighed, added with the internal standard d5-3-MCPD ester, d 5-glycidyl ester standard solution and 2ml methyl tert-butyl ether (MTBE) and vortexed for 10s to mix well. After adding 1.8mL of sulfuric acid/methanol solution, the mixture was kept at 40. + -. 1 ℃ for 16 hours with shaking. After completion of the reaction, 0.5mL of saturated sodium chloride solution was added, and the reaction was stopped by vortexing to prepare a solution to be purified.
(2) Purification
And (3) sequentially adding 2mL of sodium sulfate solution and 2mL of n-hexane into the solution to be purified, swirling, standing for 5min, layering, discarding the n-hexane, and repeatedly washing with the n-hexane for 1 time. Then 1mL of ethyl acetate/ether mixed solution is added, after layering, the upper layer solution is transferred to a glass test tube filled with a small amount of anhydrous magnesium sulfate, and extraction is repeated for 3 times until derivatization reaction.
(3) Derivatization
To the extract was added 200. mu.L of phenylboronic acid, vortexed, and allowed to stand. Nitrogen was blown to full dryness, then 500 μ L n-hexane was added for redissolution, vortexed and transferred to a sample vial by filtration through a filter.
(4) GC-MS analysis
Chromatographic conditions are as follows: keeping at 85 deg.C for 12 min; heating to 165 deg.C at a rate of 20 deg.C/min, and maintaining for 10 min; then the temperature was raised to 300 ℃ at a rate of 20 ℃/min and held for 8 min. The injection port temperature was 250 ℃. The carrier gas is high-purity helium, and the flow rate is 1 mL/min; injection volume 1. mu.L.
Mass spectrum conditions: electron impact ion source (EI) at 230 deg.C; the temperature of the quadrupole rods is 150 ℃; the scanning mode is an ion monitoring (SIM) mode.
Example 1
Heating refined corn oil sold in the market as starting oil to 60 ℃ through a heat exchanger, then feeding the refined corn oil into a thin film evaporator at a feeding rate of 700kg/h for evaporation to remove low-boiling-point substances such as water, residual solvent and the like, wherein the temperature of the thin film evaporator is 120 ℃, and obtaining oil A; and then, enabling the grease A to enter a rotary wiped film type molecular distiller through a connecting pipeline, uniformly distributing the grease A through a distributor of the rotary wiped film type molecular distiller, wherein the temperature of an evaporation surface of the molecular distiller is 210 ℃, the wiped film speed is 60r/min respectively, the temperature of a condensation surface of a built-in condenser is 40 ℃, the vacuum degree is 0.5Pa, a light component (containing an odor component) is condensed to about 40 ℃ through the built-in condenser and then flows into a light component collecting tank, a heavy component is rapidly cooled to below 60 ℃ through a heat exchanger and then enters a heavy component collecting tank, and the heavy component is the treated corn oil product.
The same process as described above was carried out under conditions of respective film-scraping rates of 100r/min, 200r/min and 300 r/min.
The detection results of 3-MCPD ester, 2-MCPD ester and glycidyl ester in the initial oil refined corn oil and the treated corn oil product are as follows:
comparative example 1
Heating refined corn oil serving as starting oil to 60 ℃ through a heat exchanger, then feeding the refined corn oil into a film evaporator at a feeding rate of 700kg/h for evaporation to remove low-boiling-point substances such as water, residual solvent and the like, wherein the temperature of the film evaporator is 120 ℃, and thus obtaining oil A; and then, enabling the grease A to enter a rotary wiped film type molecular distiller through a connecting pipeline, uniformly distributing the grease A through a distributor of the rotary wiped film type molecular distiller, wherein the temperature of an evaporation surface of the molecular distiller is 210 ℃, the wiped film rate is 40r/min, the temperature of a condensation surface of a built-in condenser is 40 ℃, the vacuum degree is 0.5Pa, a light component (containing an odor component) is condensed to 40 ℃ through the built-in condenser and then flows into a light component collecting tank, a heavy component is rapidly cooled to below 60 ℃ through a heat exchanger and then enters a heavy component collecting tank, and the heavy component is the treated corn oil product.
The same process as described above was carried out under conditions of respective wiping rates of 50r/min, 320r/min and 350 r/min.
The detection results of 3-MCPD ester, 2-MCPD ester and glycidyl ester in the initial oil refined corn oil and the treated corn oil product are as follows:
example 2
Taking refined sunflower seed oil as starting oil, heating the refined sunflower seed oil to 75 ℃ through a heat exchanger, then feeding the heated refined sunflower seed oil into a thin film evaporator at a feeding rate of 700kg/h for evaporation to remove low-boiling-point substances such as water, residual solvent and the like, wherein the temperature of the thin film evaporator is 150 ℃, and obtaining oil A; and then, enabling the grease A to enter a rotary wiped film type molecular distiller through a connecting pipeline, uniformly distributing the grease A through a distributor of the rotary wiped film type molecular distiller, wherein the temperature of an evaporation surface of the molecular distiller is 210 ℃, the wiped film rate is 200r/min, the temperature of a condensation surface of a built-in condenser is 55 ℃, the vacuum degrees are respectively 0.1Pa, light components (containing odor components) are condensed to about 55 ℃ through the built-in condenser and then flow into a light component collecting tank, the heavy components are rapidly cooled to below 60 ℃ through a heat exchanger and then enter a heavy component collecting tank, and the heavy components are the treated sunflower seed oil product.
The treatment was carried out in the same manner as described above under vacuum conditions of 0.5Pa, 10Pa, 50Pa and 100Pa, respectively.
The detection results of the 3-MCPD ester and the glycidyl ester in the initial oil refined sunflower seed oil and the treated sunflower seed oil product are as follows:
comparative example 2
Taking refined sunflower seed oil as starting oil, heating the refined sunflower seed oil to 75 ℃ through a heat exchanger, then feeding the heated refined sunflower seed oil into a thin film evaporator at a feeding rate of 700kg/h for evaporation to remove low-boiling-point substances such as water, residual solvent and the like, wherein the temperature of the thin film evaporator is 150 ℃, and obtaining oil A; and then, enabling the grease A to enter a rotary wiped film type molecular distiller through a connecting pipeline, uniformly distributing the grease A through a distributor of the rotary wiped film type molecular distiller, wherein the temperature of an evaporation surface of the molecular distiller is 210 ℃, the wiped film rate is 200r/min, the temperature of a condensation surface of a built-in condenser is 55 ℃, the vacuum degrees are respectively 0.01Pa, light components (containing odor components) are condensed to about 55 ℃ through the built-in condenser and then flow into a light component collecting tank, the heavy components are rapidly cooled to below 60 ℃ through a heat exchanger and then enter a heavy component collecting tank, and the heavy components are the treated sunflower seed oil product.
The treatment was carried out in the same manner as described above under the conditions of respective vacuum degrees of 0.05Pa, 110Pa and 150 Pa.
The detection results of the 3-MCPD ester and the glycidyl ester in the initial oil refined sunflower seed oil and the treated sunflower seed oil product are as follows:
under the condition that the vacuum degree is less than 0.1pa, although the detection value is very low, the requirement on the vacuum degree of equipment is very high, the corresponding energy consumption is also high, and the realization is difficult.
Example 3
Taking refined palm oil as starting grease, heating the refined palm oil to 90 ℃ through a heat exchanger, then feeding the refined palm oil into a thin film evaporator at a feeding rate of 300kg/h for evaporation to remove low-boiling-point substances such as water, residual solvent and the like, wherein the temperature of the thin film evaporator is 150 ℃, and obtaining grease A; and then, enabling the grease A to enter a rotary wiped film type molecular distiller through a connecting pipeline, uniformly distributing the grease A through a distributor of the rotary wiped film type molecular distiller, wherein the temperature of an evaporation surface of the molecular distiller is 190 ℃, the wiped film speed is 100r/min, the temperature of a condensation surface of a built-in condenser is 70 ℃, the temperature regulating water temperature is 70 ℃, the vacuum degree is 10Pa, a light component (containing odor components) is condensed to 70 ℃ through the built-in condenser and then flows into a light component collecting tank, a heavy component is rapidly cooled to below 60 ℃ through a heat exchanger and then enters a heavy component collecting tank, and the heavy component is a processed palm oil product.
The treatment was carried out in the same manner as described above under the conditions that the temperatures of the evaporation surfaces of the molecular distillation apparatus were 210 ℃, 230 ℃ and 270 ℃, respectively. The detection results of 3-MCPD ester and glycidyl ester in the starting oil refined palm oil and the treated palm oil product are as follows:
comparative example 3
Taking refined palm oil as starting grease, heating the refined palm oil to 90 ℃ through a heat exchanger, then feeding the refined palm oil into a thin film evaporator at a feeding rate of 300kg/h for evaporation to remove low-boiling-point substances such as water, residual solvent and the like, wherein the temperature of the thin film evaporator is 150 ℃, and obtaining grease A; and then, enabling the grease A to enter a rotary wiped film type molecular distiller through a connecting pipeline, uniformly distributing the grease A through a distributor of the rotary wiped film type molecular distiller, wherein the temperature of an evaporation surface of the molecular distiller is 170 ℃, the wiped film speed is 100r/min, the temperature of a condensation surface of a built-in condenser is 70 ℃, the vacuum degree is 10Pa, light components (containing odor components) are condensed to 70 ℃ through the built-in condenser and then flow into a light component collecting tank, the heavy components are rapidly cooled to below 60 ℃ through a heat exchanger and then enter a heavy component collecting tank, and the heavy components are the processed palm oil products.
The same process as described above was carried out under conditions of 180 ℃ and 280 ℃ for the evaporation surface of the molecular still, respectively.
The detection results of 3-MCPD ester and glycidyl ester in the starting oil refined palm oil and the treated palm oil product are as follows:
example 4
Taking refined soybean oil as starting grease, heating the refined soybean oil to 80 ℃ through a heat exchanger, then feeding the refined soybean oil into a thin film evaporator at a feeding rate of 500kg/h for evaporation to remove low-boiling-point substances such as water, residual solvent and the like, wherein the temperature of the thin film evaporator is 150 ℃, and obtaining grease A; and then, allowing the grease A to enter a rotary wiped film type molecular distiller through a connecting pipeline, uniformly distributing the grease A through a distributor of the rotary wiped film type molecular distiller, wherein the temperature of an evaporation surface of the molecular distiller is 240 ℃, the wiped film rate is 100r/min, the temperature of a condensation surface of a built-in condenser is 70 ℃, the vacuum degree is 5Pa, a light component (containing an odor component) is condensed to 70 ℃ by the built-in condenser and then flows into a light component collecting tank, a heavy component is rapidly cooled to below 60 ℃ by a heat exchanger and then enters a heavy component collecting tank, and the heavy component is a processed soybean oil product.
The detection results of 3-MCPD ester and glycidyl ester in the starting oil refined soybean oil and the treated soybean oil product are as follows:
comparative example 4
Taking refined soybean oil as starting grease, heating the refined soybean oil to 80 ℃ through a heat exchanger, then feeding the refined soybean oil into a thin film evaporator at a feeding rate of 500kg/h for evaporation to remove low-boiling-point substances such as water, residual solvent and the like, wherein the temperature of the thin film evaporator is 150 ℃, and obtaining grease A; and then, allowing the grease A to enter a rotary wiped film type molecular distiller through a connecting pipeline, uniformly distributing the grease A through a distributor of the rotary wiped film type molecular distiller, wherein the temperature of an evaporation surface of the molecular distiller is 240 ℃, the wiped film rate is 100r/min, the temperature of a condensation surface of a built-in condenser is 70 ℃, the vacuum degree is 110Pa, a light component (containing an odor component) is condensed to 70 ℃ by the built-in condenser and then flows into a light component collecting tank, a heavy component is rapidly cooled to below 60 ℃ by a heat exchanger and then enters a heavy component collecting tank, and the heavy component is a processed soybean oil product.
The detection results of 3-MCPD ester and glycidyl ester in the starting oil refined soybean oil and the treated soybean oil product are as follows:
example 5
Taking refined rice oil as starting grease, heating the refined rice oil to 75 ℃ through a heat exchanger, then feeding the refined rice oil into a thin film evaporator at a feeding rate of 500kg/h for evaporation to remove low-boiling-point substances such as water, residual solvent and the like, wherein the temperature of the thin film evaporator is 120 ℃, and obtaining grease A; and then the grease A enters a rotary wiped film type molecular distiller through a connecting pipeline, the grease A is uniformly distributed through a distributor of the rotary wiped film type molecular distiller, the temperature of an evaporation surface of the molecular distiller is 230 ℃, the wiped film speed is 300r/min, the temperature of a condensation surface of a built-in condenser is 50 ℃, the vacuum degree is 50Pa, light components (containing odor components) are condensed to 50 ℃ through the built-in condenser and then flow into a light component collecting tank, the heavy components are rapidly cooled to below 60 ℃ through a heat exchanger and then enter a heavy component collecting tank, and the heavy components are the treated rice oil product.
The detection results of 3-MCPD ester and glycidyl ester in the initial oil refined rice oil and the treated rice oil product are as follows:
comparative example 5
Taking refined rice oil as starting grease, heating the refined rice oil raw material to 75 ℃ through a heat exchanger, then feeding the refined rice oil raw material into a thin film evaporator at a feeding rate of 500kg/h for evaporation to remove low-boiling-point substances such as water, residual solvent and the like, wherein the temperature of the thin film evaporator is 120 ℃, and obtaining grease A; and then the grease A enters a rotary wiped film type molecular distiller through a connecting pipeline, the grease A is uniformly distributed through a distributor of the rotary wiped film type molecular distiller, the temperature of an evaporation surface of the molecular distiller is 180 ℃, the wiped film speed is 300r/min, the temperature of a condensation surface of a built-in condenser is 50 ℃, the vacuum degree is 50Pa, light components (containing odor components) are condensed to 50 ℃ through the built-in condenser and then flow into a light component collecting tank, the heavy components are rapidly cooled to below 60 ℃ through a heat exchanger and then enter a heavy component collecting tank, and the heavy components are the treated rice oil product.
The detection results of 3-MCPD ester and glycidyl ester in the initial oil refined rice oil and the treated rice oil product are as follows:
example 6
Heating refined coconut oil to 75 ℃ through a heat exchanger by taking the refined coconut oil as starting oil, then feeding the refined coconut oil into a thin film evaporator at a feeding rate of 500kg/h for evaporation to remove low-boiling-point substances such as water, residual solvent and the like, wherein the temperature of the thin film evaporator is 150 ℃, and obtaining oil A; and then, enabling the grease A to enter a rotary wiped film type molecular distiller through a connecting pipeline, uniformly distributing the grease A through a distributor of the rotary wiped film type molecular distiller, wherein the temperature of an evaporation surface of the molecular distiller is 200 ℃, the wiped film rate is 100r/min, the temperature of a condensation surface of a built-in condenser is 50 ℃, the vacuum degree is 100Pa, light components (containing odor components) are condensed to about 50 ℃ through the built-in condenser and then flow into a light component collecting tank, the heavy components are rapidly cooled to below 60 ℃ through a heat exchanger and then enter a heavy component collecting tank, and the heavy components are the treated coconut oil product.
The results of 3-MCPD esters, 2-MCPD esters, and glycidyl esters in the starting oil refined coconut oil and the treated coconut oil product are as follows:
comparative example 6
Heating refined coconut oil to 75 ℃ through a heat exchanger by taking the refined coconut oil as starting oil, then feeding the refined coconut oil into a thin film evaporator at a feeding rate of 500kg/h for evaporation to remove low-boiling-point substances such as water, residual solvent and the like, wherein the temperature of the thin film evaporator is 150 ℃, and obtaining oil A; and then, enabling the grease A to enter a rotary wiped film type molecular distiller through a connecting pipeline, uniformly distributing the grease A through a distributor of the rotary wiped film type molecular distiller, wherein the temperature of an evaporation surface of the molecular distiller is 200 ℃, the wiped film rate is 100r/min, the temperature of a condensation surface of a built-in condenser is 50 ℃, the vacuum degree is 110Pa, light components (containing odor components) are condensed to 50 ℃ through the built-in condenser and then flow into a light component collecting tank, the heavy components are rapidly cooled to below 60 ℃ through a heat exchanger and then enter a heavy component collecting tank, and the heavy components are the treated coconut oil product.
The results of 3-MCPD esters, 2-MCPD esters, and glycidyl esters in the starting oil refined coconut oil and the treated coconut oil product are as follows:
from the results of the above examples and comparative examples, it can be seen that the contents of the three substances, 3-MCPD ester, 2-MCPD ester and glycidyl ester, in the edible fat and oil can be simultaneously reduced by using the rotary wiped film type molecular still in combination with the process conditions within the optimum range of the present invention. The method is simple to operate, high in practicability and more suitable for application of oil processing enterprises, and healthier edible oil can be produced.
Claims (8)
1. A method of reducing the content of 3-MCPD esters, 2-MCPD esters, and glycidyl esters in an edible oil or fat, the method comprising:
heating the starting grease to 60-90 ℃, preferably 70-85 ℃, feeding the starting grease into a thin film evaporator at a feeding rate of 300kg/h-700kg/h, preferably 300kg/h-500kg/h for evaporation to obtain grease A, wherein the temperature of the thin film evaporator is 120-180 ℃, preferably 130-150 ℃;
and (2) allowing the grease A to enter a rotary wiped film type molecular distiller for molecular distillation to obtain a light component and a heavy component, wherein the heavy component is a grease product, the temperature of an evaporation surface of the rotary wiped film type molecular distiller is 190-270 ℃, preferably 210-270 ℃, further preferably 230-240 ℃, the wiped film rate is 60-300 r/min, preferably 100-200 r/min, and the vacuum degree is 0.1-100 Pa, preferably 0.5-50 Pa.
2. The method of claim 1, wherein the starting oil is a refined vegetable or animal oil selected from one or more of the group consisting of: corn oil, sunflower seed oil, palm oil, soybean oil, rice oil, palm olein, palm stearin, palm oil medium melting point fraction, palm olein, palm kernel oil, coconut oil, rapeseed oil, cottonseed oil, safflower seed oil, high oleic sunflower oil, high oleic soybean oil, hazelnut oil, tea seed oil, olive oil, wheat germ oil, sesame oil, algae oil, grape seed oil, safflower oil, perilla seed oil, beef tallow, lard, chicken oil, butter, fish oil, whale oil, sheep oil, and modified oils obtained by extremely hydrogenating and fractionating these oils.
3. A process according to claim 1 or 2, wherein the starting grease is warmed by passing it through a heat exchanger.
4. A method according to any one of claims 1 to 3, wherein the moisture content of the fat a is 0.2 wt% or less, preferably 0.15 wt% or less.
5. The method according to any one of claims 1 to 4, wherein the fat A has a n-hexane content of 20mg/kg or less, preferably 15mg/kg or less.
6. The process of any one of claims 1-5, wherein the heavy fraction is cooled to below 60 ℃ and collected, and the heavy fraction is cooled by a heat exchanger.
7. The method according to any one of claims 1 to 6, wherein the light fraction is reduced in temperature by an internal condenser of the rotary wiped film molecular still, the internal condenser having a condensing surface temperature of 40 ℃ to 70 ℃.
8. The method according to any one of claims 1 to 7, wherein the content of 3-MCPD ester, 2-MCPD ester and glycidyl ester in the grease product is 1.0ppm or less, preferably 0.5ppm or less, further preferably 0.3ppm or less.
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| CN111426780A (en) * | 2020-04-23 | 2020-07-17 | 华南理工大学 | Method for parallel detection of chloropropanol ester and glycidyl ester in grease |
| CN111763566A (en) * | 2020-07-24 | 2020-10-13 | 无锡中粮工程科技有限公司 | Deodorization system and deodorization process for reducing glycidyl ester and plasticizer of vegetable oil |
| CN113337338A (en) * | 2021-05-17 | 2021-09-03 | 辽宁晟麦实业股份有限公司 | Method for reducing mineral oil in edible vegetable oil |
| CN114516852A (en) * | 2022-03-08 | 2022-05-20 | 陕西海斯夫生物工程有限公司 | Method for removing glycidyl ester, 3-chloropropanediol and ester thereof from natural vitamin E and obtained product |
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| CN103525550A (en) * | 2013-10-15 | 2014-01-22 | 江南大学 | Deodorization method used for lowering content of 3-chlorine-1,2-propylene glycol in vegetable oil |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111426780A (en) * | 2020-04-23 | 2020-07-17 | 华南理工大学 | Method for parallel detection of chloropropanol ester and glycidyl ester in grease |
| CN111763566A (en) * | 2020-07-24 | 2020-10-13 | 无锡中粮工程科技有限公司 | Deodorization system and deodorization process for reducing glycidyl ester and plasticizer of vegetable oil |
| CN113337338A (en) * | 2021-05-17 | 2021-09-03 | 辽宁晟麦实业股份有限公司 | Method for reducing mineral oil in edible vegetable oil |
| WO2022242102A1 (en) * | 2021-05-17 | 2022-11-24 | 辽宁晟麦实业股份有限公司 | Method for reducing mineral oils in edible vegetable oil |
| CN113337338B (en) * | 2021-05-17 | 2024-02-02 | 辽宁晟麦实业股份有限公司 | Method for reducing mineral oil in edible vegetable oil |
| CN114516852A (en) * | 2022-03-08 | 2022-05-20 | 陕西海斯夫生物工程有限公司 | Method for removing glycidyl ester, 3-chloropropanediol and ester thereof from natural vitamin E and obtained product |
| CN114516852B (en) * | 2022-03-08 | 2022-11-01 | 陕西海斯夫生物工程有限公司 | Method for removing glycidyl ester, 3-chloropropanediol and ester thereof from natural vitamin E and obtained product |
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