CN111349513B - Processing technology for controlling generation of 3-MCPD ester and glycidyl ester in edible oil - Google Patents

Processing technology for controlling generation of 3-MCPD ester and glycidyl ester in edible oil Download PDF

Info

Publication number
CN111349513B
CN111349513B CN202010170379.6A CN202010170379A CN111349513B CN 111349513 B CN111349513 B CN 111349513B CN 202010170379 A CN202010170379 A CN 202010170379A CN 111349513 B CN111349513 B CN 111349513B
Authority
CN
China
Prior art keywords
oil
oil phase
temperature
ester
edible oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010170379.6A
Other languages
Chinese (zh)
Other versions
CN111349513A (en
Inventor
于小华
于强
杨增龙
宋福荣
王青
孔德程
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao Tianxiang Foods Group
Original Assignee
Qingdao Tianxiang Foods Group
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qingdao Tianxiang Foods Group filed Critical Qingdao Tianxiang Foods Group
Priority to CN202010170379.6A priority Critical patent/CN111349513B/en
Publication of CN111349513A publication Critical patent/CN111349513A/en
Application granted granted Critical
Publication of CN111349513B publication Critical patent/CN111349513B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00Refining fats or fatty oils
    • C11B3/001Refining fats or fatty oils by a combination of two or more of the means hereafter
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00Refining fats or fatty oils
    • C11B3/008Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00Refining fats or fatty oils
    • C11B3/10Refining fats or fatty oils by adsorption
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00Refining fats or fatty oils
    • C11B3/16Refining fats or fatty oils by mechanical means
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/62Plastics recycling; Rubber recycling
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/74Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Fats And Perfumes (AREA)

Abstract

The invention belongs to the technical field of edible oil processing, and relates to a processing technology for controlling generation of 3-MCPD ester and glycidyl ester in edible oil, which comprises the following steps: (1) Filtering the crude oil, adding a mixed auxiliary agent, stirring and mixing at normal temperature, performing ultrasonic treatment, and performing centrifugal separation to obtain an oil phase; (2) Adding a mixed auxiliary agent into the oil phase obtained in the step (1), stirring and mixing at normal temperature, performing ultrasonic treatment, and performing centrifugal separation to obtain an oil phase; repeating the operation for 6 times; (3) Adding silica gel into the oil phase edible oil obtained after centrifugation in the step (2) for degumming, performing centrifugal separation to obtain an oil phase, repeating twice, filtering the obtained oil phase, decoloring, performing secondary filtration, deodorizing the edible oil at low temperature, and then entering a deacidification device for low-temperature rapid deacidification to obtain the finished oil. The process can remove the plasticizer in the early stage, and a high-temperature distillation step is not required in the later stage, so that the formation of glycidyl ester and 3-MCPD ester caused by high temperature is avoided.

Description

Processing technology for controlling generation of 3-MCPD ester and glycidyl ester in edible oil
Technical Field
The invention belongs to the technical field of edible oil processing, and particularly relates to a processing technology for controlling generation of 3-MCPD ester and glycidyl ester in edible oil.
Background
At present in agricultural production, the use of a large amount of plastic films for during plasticizer passes through soil migration entering oil, the burning of a large amount of plastic products rubbish in addition leads to the air to be contaminated by plasticizer, thereby makes the oil contaminated by the plasticizer in the air at the planting process, causes edible oil plasticizer too high. The plasticizer is a general name of phthalate, is a chemical high polymer material auxiliary agent, is also called as a plasticizer, has strong toxicity to liver, kidney, lung, heart, reproductive system and the like, and has risks of teratogenesis, carcinogenesis, immunosuppression and the like. At present, most of edible crude oil contains plasticizers which are seriously out of standard, wherein the sources of the plasticizers mainly comprise environmental pollution, non-compliant plastic packaging materials, irregular processing processes and the like. The plasticizer is fat-soluble and is mutually soluble with the edible oil, in the prior art, the fat processing technology mostly adopts high-temperature distillation to remove the plasticizer, but the edible oil after high temperature is easy to produce 3-MCPD ester and glycidyl ester. 3-MCPD ester and glycidyl ester enter a human body to form 3-chloropropanediol and glycidol, and both hazards are internationally recognized genetic carcinogens. In common vegetable oil esters, due to the fact that the refining temperature is too high, the content of 3-MCPD esters and glycidyl esters in the edible oil is far beyond the safety standard, and therefore, an optimized edible oil processing technology is urgently needed, the plasticizer is removed, and meanwhile the generation of the 3-MCPD esters and the glycidyl esters is controlled, so that the safety of the edible oil is improved. In the determination of phthalate in food of national standard GB 5009.271, the detection method of 18 phthalate substances is specified.
The existing method for removing the plasticizer mainly comprises a physical adsorption removal method and a high-temperature distillation removal method. Physical adsorption and removal are carried out by adopting an adsorbent, in the patent with the publication number of CN109880688A, physical adsorption of activated carbon, silicate, activated alumina, activated clay and the like only has an effect on a plurality of phthalic acid esters with small content, but has no obvious effect on common harmful dibutyl phthalate (DBP), di (2-ethylhexyl) phthalate (DEHP) and diisononyl phthalate (DINP). And when the 3-MCPD ester and the glycidyl ester (CN 104694250A) are removed by physical adsorption, foreign matters are easily introduced by physical adsorption, so that the risk and the processing cost are increased. In the method for removing the plasticizer by high-temperature distillation, the high temperature adopted is higher than 250 ℃ (CN 105925371A), which can cause the generation of 3-MCPD ester and glycidyl ester.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a processing technology for controlling the generation of 3-MCPD ester and glycidyl ester in edible oil, which can remove plasticizer in the early stage of the processing technology and does not need a high-temperature distillation step in the later stage, thereby avoiding the formation of glycidyl ester and 3-MCPD ester caused by high temperature.
The technical scheme of the invention is as follows:
a process for controlling the production of 3-MCPD esters and glycidyl esters in edible oils comprising the steps of:
(1) Filtering the crude oil, adding a mixed auxiliary agent into the filtered crude oil, stirring and performing ultrasonic treatment at normal temperature, performing centrifugal separation, and removing subnatant to obtain an oil phase;
(2) Adding a mixed auxiliary agent into the oil phase obtained in the step (1), stirring and mixing at normal temperature, performing ultrasonic treatment, and performing centrifugal separation to obtain an oil phase; repeating the operation for 6 times;
(3) Adding silica gel into the oil-phase edible oil obtained after centrifugation in the step (2) for degumming, performing centrifugal separation to obtain an oil phase, repeating twice, filtering the obtained oil phase, decoloring, performing secondary filtration, deodorizing the edible oil at low temperature, and then entering a deacidification device for low-temperature rapid deacidification to obtain the finished oil.
In the steps, the plasticizer is not well adsorbed due to poor intersolubility of water, activated clay and silica gel with the oil, and the plasticizer in the oil is extracted out by alcohol and is mutually dissolved with water, so that the content of the plasticizer in the oil phase is greatly reduced; the plasticizer dissolved in the alcohol is adsorbed and removed under the synergistic action of the silica gel and the activated clay, and the removal rate of the plasticizer is up to more than 90 percent through filtration and repeated action.
Further, the components of the mixing auxiliary agent comprise water, activated clay, silica gel and alcohol; sequentially adding water, activated clay, silica gel and alcohol into the crude oil, wherein the weight of each component is as follows: weighing water in an amount of 15-20% of the weight of the crude oil, weighing activated clay in an amount of 0.5-1.5 per mill of the weight of the crude oil, weighing silica gel in an amount of 0.5-2.0 per mill of the weight of the crude oil, and weighing alcohol in an amount of 2.0-4.0% of the weight of the crude oil.
Further, the stirring time is 25-35 min, and the ultrasonic time is 25-35 min.
Further, the addition amount of the silica gel in the step (3) is one thousandth of the mass of the oil phase.
Further, the deodorization temperature in the step (3) is 230-245 ℃, and the deodorization time is 12-18 min.
Further, the deacidification temperature in the step (3) is 220-240 ℃.
The invention has the beneficial effects that:
because the crude oil contains the plasticizer, the plasticizer is removed at high temperature in the prior art, and the generation of glycidyl ester and 3-MCPD ester can be caused. The edible oil obtained by adopting the process steps of the invention meets the regulation that 3-MCPD in FDA recommended food should not exceed 1mg/kg dry matter.
Drawings
FIG. 1 is a process flow diagram provided by an embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be described in detail and fully with reference to the following specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention.
For a further understanding of the present invention, reference will now be made in detail to the present invention with reference to the following examples.
Example 1
A process for controlling the production of 3-MCPD esters and glycidyl esters in edible oils, comprising the steps of:
(1) Filtering the crude oil, and adding a mixed auxiliary agent into the crude oil, wherein the mixed auxiliary agent comprises water, activated clay, silica gel and alcohol; sequentially adding 18%, 1.0% and 4.0% of the crude oil into the crude oil, stirring at normal temperature for 25-35 min, performing ultrasonic treatment for 25-35 min, centrifuging, and removing subnatant to obtain an oil phase;
(2) Adding the mixed auxiliary agent obtained in the step (1) into the oil phase obtained in the step (1), stirring for 25-35 min at normal temperature, mixing, performing ultrasonic treatment for 25-35 min, and performing centrifugal separation to obtain an oil phase; repeating the operation for 6 times;
(3) Adding one thousandth of silica gel of the weight of the edible oil into the oil-phase edible oil obtained after centrifugation in the step (2), degumming, performing centrifugal separation to obtain an oil phase, repeating twice, filtering the obtained oil phase, decoloring, filtering again, heating the filtered edible oil to 230 ℃, performing low-temperature deodorization for 12-18 min, then entering a deacidification device, setting the deacidification temperature at 220 ℃, performing low-temperature rapid deacidification, wherein the deacidification time is 25-30 s, and performing deacidification and cooling to obtain a finished oil product, namely the finished oil product with high safety.
Example 2
A process for controlling the production of 3-MCPD esters and glycidyl esters in edible oils, comprising the steps of:
(1) Filtering the crude oil, and adding a mixed auxiliary agent into the crude oil, wherein the mixed auxiliary agent comprises water, activated clay, silica gel and alcohol; adding the components into the crude oil according to the weight of 15%, 0.5% and 2.0% of the crude oil in turn, stirring at normal temperature for 25-35 min, performing ultrasonic treatment for 25-35 min, performing centrifugal separation, and removing subnatant to obtain an oil phase;
(2) Adding the mixed auxiliary agent obtained in the step (1) into the oil phase obtained in the step (1), stirring for 25-35 min at normal temperature, mixing, performing ultrasonic treatment for 25-35 min, and performing centrifugal separation to obtain an oil phase; repeating the operation for 6 times;
(3) Adding one thousandth of silica gel of the weight of the edible oil into the oil-phase edible oil obtained after centrifugation in the step (2), degumming, performing centrifugal separation to obtain an oil phase, repeating twice, filtering the obtained oil phase, decoloring, filtering again, heating the filtered edible oil to 245 ℃, performing low-temperature deodorization for 12-18 min, then entering a deacidification device, setting the deacidification temperature to 240 ℃, performing low-temperature rapid deacidification, and performing deacidification and cooling for 25-30 s to obtain the finished oil, thus obtaining the finished oil with high safety.
Example 3
A process for controlling the production of 3-MCPD esters and glycidyl esters in edible oils, comprising the steps of:
(1) Filtering the crude oil, and adding a mixed auxiliary agent into the crude oil, wherein the mixed auxiliary agent comprises water, activated clay, silica gel and alcohol; sequentially adding the components into the crude oil according to the weight of 20%, 1.5%, 2.0% and 3.0% of the crude oil respectively, stirring at normal temperature for 25-35 min, performing ultrasonic treatment for 25-35 min, then performing centrifugal separation on the mixture, and removing subnatant to obtain an oil phase;
(2) Adding the mixed auxiliary agent obtained in the step (1) into the oil phase obtained in the step (1), stirring for 25-35 min at normal temperature, mixing, performing ultrasonic treatment for 25-35 min, and performing centrifugal separation to obtain an oil phase; repeating the operation for 6 times;
(3) And (3) adding one thousandth of silica gel of the weight of the edible oil into the oil-phase edible oil obtained after centrifugation in the step (2), degumming, performing centrifugal separation to obtain an oil phase, repeating twice, filtering the obtained oil phase, decoloring, filtering again, heating the filtered edible oil to 235 ℃, performing low-temperature deodorization for 12-18 min, then entering a deacidification device, setting the deacidification temperature to be 230 ℃, performing low-temperature rapid deacidification for 25-30 s, and performing deacidification and cooling to obtain a finished oil product, namely the finished oil product with high safety.
The above description is only for the preferred embodiment of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements and the like made within the scope of the present invention should be included in the patent protection scope of the present invention.

Claims (5)

1. The processing technology for controlling the generation of the 3-MCPD ester and the glycidyl ester in the edible oil is characterized by comprising the following steps:
(1) Filtering the crude oil, adding a mixed auxiliary agent, stirring and mixing at normal temperature, performing ultrasonic treatment, and performing centrifugal separation to obtain an oil phase;
the mixed auxiliary agent comprises water, activated clay, silica gel and alcohol; the components are respectively added into the crude oil according to 15 to 20 percent, 0.5 to 1.5 thousandths, 0.5 to 2.0 thousandths and 2.0 to 4.0 percent of the weight of the crude oil in turn;
(2) Adding a mixed auxiliary agent into the oil phase obtained in the step (1), stirring and mixing at normal temperature, performing ultrasonic treatment, and performing centrifugal separation to obtain an oil phase; repeating the operation for 6 times;
(3) Adding silica gel into the oil phase edible oil obtained after centrifugation in the step (2) for degumming, performing centrifugal separation to obtain an oil phase, repeating twice, filtering the obtained oil phase, decoloring, performing secondary filtration, deodorizing the edible oil at low temperature, and then entering a deacidification device for low-temperature rapid deacidification to obtain the finished oil.
2. The process according to claim 1, wherein the stirring time is 25 to 35min and the ultrasound time is 25 to 35min.
3. The process according to claim 1, wherein the amount of silica gel added in step (3) is one thousandth of the mass of the oil phase.
4. The process according to claim 1, wherein the deodorization temperature in the step (3) is 230 to 245 ℃ and the deodorization time is 12 to 18min.
5. The process according to claim 1, wherein the deacidification temperature in step (3) is 220 to 240 ℃.
CN202010170379.6A 2020-03-12 2020-03-12 Processing technology for controlling generation of 3-MCPD ester and glycidyl ester in edible oil Active CN111349513B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010170379.6A CN111349513B (en) 2020-03-12 2020-03-12 Processing technology for controlling generation of 3-MCPD ester and glycidyl ester in edible oil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010170379.6A CN111349513B (en) 2020-03-12 2020-03-12 Processing technology for controlling generation of 3-MCPD ester and glycidyl ester in edible oil

Publications (2)

Publication Number Publication Date
CN111349513A CN111349513A (en) 2020-06-30
CN111349513B true CN111349513B (en) 2023-03-17

Family

ID=71190698

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010170379.6A Active CN111349513B (en) 2020-03-12 2020-03-12 Processing technology for controlling generation of 3-MCPD ester and glycidyl ester in edible oil

Country Status (1)

Country Link
CN (1) CN111349513B (en)

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5700503B2 (en) * 2009-09-07 2015-04-15 日清オイリオグループ株式会社 Glyceride composition and method for producing the glyceride composition
CN102334563B (en) * 2010-07-16 2015-03-25 丰益(上海)生物技术研发中心有限公司 Method for controlling content of 3-chloro-1,2-propanediol or ester thereof in oil
CN103589511B (en) * 2012-01-21 2015-11-18 上海好油工业设备有限公司 A kind of degumming process for edible vegetable oil and application thereof
CN103908946B (en) * 2013-01-07 2018-04-06 丰益(上海)生物技术研发中心有限公司 A kind of mixed adsorbent, grease and preparation method thereof
CN103382413B (en) * 2013-07-16 2015-03-11 傅武胜 Refining process for reducing content of MCPD in tea seed oil
CN104694250B (en) * 2013-12-10 2020-02-04 丰益(上海)生物技术研发中心有限公司 Method for reducing 3-MCPD ester and/or glycidyl ester in grease
CN105176676A (en) * 2015-07-17 2015-12-23 广州市正德生物科技有限公司 Edible plant oil non-soap refining method
CN108239573A (en) * 2016-12-27 2018-07-03 中粮集团有限公司 Grease and preparation method thereof
CN107090353B (en) * 2017-05-04 2021-03-09 辽宁晟麦实业股份有限公司 Method for reducing content of glycidyl ester in refined vegetable oil
CN110760377A (en) * 2019-11-15 2020-02-07 湖南省康多利油脂有限公司 Preparation method of plasticizer-removed tea oil
CN110760382A (en) * 2019-12-10 2020-02-07 海南省粮油科学研究所 Refining method of crabapple seed crude oil

Also Published As

Publication number Publication date
CN111349513A (en) 2020-06-30

Similar Documents

Publication Publication Date Title
CN106367208B (en) A kind of isolation and purification method of galic essential oil
CN101379174B (en) Process for production of highly enriched fractions of natural compounds from palm oil with supercritical and near critical fluids
CN104694250B (en) Method for reducing 3-MCPD ester and/or glycidyl ester in grease
CN103614237A (en) Rapeseed crude oil refining process
US4154750A (en) Activated carbon improved vegetable oil refining process
JP2008255231A (en) Simultaneous production method of fucoxanthine and fucoidan
CN107090353B (en) Method for reducing content of glycidyl ester in refined vegetable oil
CN110760377A (en) Preparation method of plasticizer-removed tea oil
CN111349513B (en) Processing technology for controlling generation of 3-MCPD ester and glycidyl ester in edible oil
CN103787864B (en) Method for extracting DHA (Docosahexaenoic acid) from marine microalgae fermentation liquor
JP6396399B2 (en) Palm oil with reduced saturated hydrocarbon content
CN106929148A (en) The method of oil and fat refining
CN111518616A (en) Refining method of camellia seed oil
CN100363378C (en) Method for producing mixture of phytosterol and vitamin E
CN109880688A (en) The preparation method of low plasticiser or the grease without plasticiser
CN101831349B (en) Method for extracting wheat-germ oil continuously by using microwave secondary solvent
US9200029B2 (en) Process for production of triterpene alcohol
JP5272073B2 (en) Method for producing tocotrienol composition
CN106867660A (en) A kind of purification method of rice bran miscella
CN106398865A (en) Method for continuously treating illegal cooking oil
CN108822176A (en) A kind of technique that enzyme process esterification free fatty acid extracts phytosterol
CN111286400A (en) Preparation method of microalgae oil DHA product capable of reducing 3-chloro-1, 2-propanediol content
CN113046170B (en) Preparation method and application of avocado oil rich in furan lipid unsaponifiable matter
CN103992256B (en) A kind of method preparing high-purity lutein ester from pot marigold
CN109022129A (en) A kind of production method of camellia seed oil

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant