CN106769235B - A kind of environmental contaminants time series concentration passive type sampling apparatus - Google Patents
A kind of environmental contaminants time series concentration passive type sampling apparatus Download PDFInfo
- Publication number
- CN106769235B CN106769235B CN201611037115.3A CN201611037115A CN106769235B CN 106769235 B CN106769235 B CN 106769235B CN 201611037115 A CN201611037115 A CN 201611037115A CN 106769235 B CN106769235 B CN 106769235B
- Authority
- CN
- China
- Prior art keywords
- coil pipe
- phase coil
- time series
- phase
- reception
- 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
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2273—Atmospheric sampling
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/10—Devices for withdrawing samples in the liquid or fluent state
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention discloses a kind of environmental contaminants time series concentration passive type sampling apparatuses, preceding reception phase coil pipe, the rear reception phase coil pipe of FEP, a PTFE or stainless steel material and the antipriming pipe of a ceramics or plastics material including an osmotic pumps, FEP, a PTFE or stainless steel material.The present invention is using osmotic pumps as power, driving receives the reception phase in phase coil pipe before being stored in, it is set to continue to flow through antipriming pipe, absorb the pollutant in atmosphere or water body, reception after absorbing pollutant receives in phase coil pipe after being mutually stored in, the continuous absorption to pollutant and preservation are realized, the amount of the pollutant in the reception phase in phase coil pipe is received after being stored in eventually by analysis, to obtain the data i.e. time series data of the concentration changes with time of pollutant in atmosphere or water body.
Description
Technical field
The invention belongs to enviromental monitoring equipment technical fields, and in particular to a kind of environmental contaminants time series concentration is passive
Formula sampling apparatus.
Background technique
Passive sample devices are generally mutually formed with diffusion restricting membrane by receiving.Reception mutually can be solvent, chemical reagent or
Solid absorbent.Diffusion restricting membrane can slow down target compound and receive the accumulative speed in phase, and limit Cucumber transmission,
Make sampler that there is certain selectivity.Passive sample devices receive the freedom of phase based on pollutant from surrounding medium to sampler
Diffusion process, driving force are the difference of chemical potential of the pollutant between surrounding medium and reception phase.Sampler cloth is placed on
It is recycled after a period of time in environment, measurement receives the total amount of pollutant being enriched in phase, in conjunction with the sampling time and in advance in laboratory
The time mean concentration of sampling period pollutant can be calculated in the sampling rate measured.Existing passive sample devices are main
Including semipermeable membrane devices (SPMD), diffusion film (DGT), chemical collecting devicePolarity is organic
Object integrated sampling device (POCIS) etc..Passive sampler can carry out continuous monitoring, be not necessarily to external impetus, lay conveniently,
The various pollutants being widely used in water body or atmospheric environment at present such as trace metal, all kinds of pesticides, resists polycyclic aromatic hydrocarbon
The sampling monitoring of raw element, ammonia, formaldehyde and volatile organic compounds etc..
The concentration of pollutant in the environment changes at any time, and the data i.e. time series for obtaining concentration changes with time is dense
Degree is according to the change procedure that could accurately characterize pollutant in environment.However, the reception in existing Passive sampler mutually exists
Sampling period be it is non-renewable, often lay and once can only obtain a time mean concentration, environment can not be obtained using them
The time series concentration of middle pollutant, cannot achieve to some fast-changing processes as burst contamination accident, Solar diurnal variation,
The accurate measurements of flood, storm, wawter bloom event, tide etc..
Summary of the invention
It is an object of the invention to overcome prior art defect, a kind of environmental contaminants time series concentration passive type is provided
Sampling apparatus.
Technical scheme is as follows:
A kind of environmental contaminants time series concentration passive type sampling apparatus, including
One osmotic pumps, the seal casinghousing including an organic glass material, the seal casinghousing is interior to have a reverse osmosis membrane, will be close
Capsule body is divided into the output cavity for filling saturated sodium chloride solution and solid sodium chloride and one and fills distilled water and ion exchange
The input cavity of resin；
The preceding reception phase coil pipe of one FEP, PTFE or stainless steel material, liquid feeding end are connected to the output cavity of osmotic pumps, in
Reception phase is stored in advance；
The rear reception phase coil pipe of one FEP, PTFE or stainless steel material, outlet end are connected to the input cavity of osmotic pumps, in
Distilled water is stored in advance；
With the antipriming pipe of a porous ceramics or plastic material, the outlet end of phase coil pipe is received before being connected to and receives phase coil pipe afterwards
Liquid feeding end.
In a preferred embodiment of the invention, the reception is mutually acid or the aqueous solution of alkali, to acquire environment
In inorganic pollution.
It is further preferred that between different from the physicochemical properties of phase are received with spaced in the reception phase
Parting matter.
In a preferred embodiment of the invention, the reception is mutually alkane or aromatic hydrocarbons, to acquire in environment
Organic pollutant.
It is further preferred that between different from the physicochemical properties of phase are received with spaced in the reception phase
Parting matter.
It is equipped with a detection unit between phase coil pipe liquid feeding end and the antipriming pipe it is further preferred that receiving after described, uses
The time that detection unit is mutually crossed with interval material stream is received to determine.
It is further preferred that the detection unit is micro conductivity instrument or microspectrophotometer.
Beneficial effects of the present invention:
1, for the present invention using osmotic pumps as power, driving receives the reception phase in phase coil pipe before being stored in, and continues to flow through it
Antipriming pipe absorbs the pollutant in atmosphere or water body, and the reception after absorbing pollutant receives in phase coil pipe after being mutually stored in, real
The continuous absorption to pollutant and preservation are showed, the pollution in the reception phase in phase coil pipe are received after being stored in eventually by analysis
The amount of object, to obtain the data i.e. time series data of the concentration changes with time of pollutant.
2, the present invention uses osmotic pumps, supplies without external power, small in size, light-weight, is suitable for prolonged field
Sampling.
3, the reception in preceding reception phase coil pipe is mutually separated into section using interval substance by the present invention, and in rear reception phase coil pipe
Entrance install detection unit, using interval substance and receive phase physicochemical properties difference, accurate measurements reception mutually flows
Spend the time of antipriming pipe, i.e. sampling time.
Detailed description of the invention
Fig. 1 is the structural representation of the environmental contaminants time series concentration passive type sampling apparatus of the embodiment of the present invention 1 and 2
Figure.
Fig. 2 is the structural representation of the environmental contaminants time series concentration passive type sampling apparatus of the embodiment of the present invention 3 and 4
Figure.
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment combination attached drawing.
Embodiment 1
As shown in Figure 1, a kind of environmental contaminants time series concentration passive type sampling apparatus, including an osmotic pumps 1, one
The rear reception phase coil pipe 3 and one of FEP, PTFE or the preceding reception phase coil pipe 2 of stainless steel material, FEP, a PTFE or stainless steel material
The antipriming pipe 4 of porous ceramics or plastic material (preferably AF2400).
Osmotic pumps 1, the seal casinghousing 10 including an organic glass material, the seal casinghousing 10 is interior to have a reverse osmosis membrane
11, divide the output cavity 15 and one for filling saturated sodium chloride solution 12 for one to fill distilled water and amberlite seal casinghousing 10
The input cavity 16 of rouge 13, wherein the specification of reverse osmosis membrane 11 is determined by the sampling flow velocity needed, is contained in saturated sodium chloride solution 12
There are a large amount of solid sodium chlorides, preferred polishing resin (such as Tao Shi DOWEX of ion exchange resin 13TM)；
Preceding reception phase coil pipe 2, liquid feeding end are connected to the output cavity 15 of osmotic pumps 1, and interior store in advance receives phase 21, should
Receiving phase 21 is alkane (such as n-hexane) or aromatic hydrocarbons (such as toluene), that is to say, that the present embodiment is used to detect organic dirt in environment
Contaminate object；
Phase coil pipe 3 is received afterwards, and outlet end is connected to the input cavity 16 of osmotic pumps 1, interior to store distilled water in advance；
Antipriming pipe 4 receives the outlet end and the rear liquid feeding end for receiving phase coil pipe 3 of phase coil pipe 2 before being connected to.
The course of work is specific as follows: being put into ion exchange resin 13 and distilled water in the input cavity 16 of osmotic pumps 1, is seeping
It is put into saturated sodium chloride solution and solid sodium chloride 12 in the output cavity 15 of pump 1 thoroughly, is filled with reception phase in preceding reception phase coil pipe 2
21, it is filled with distilled water in rear reception phase coil pipe 3, connects all parts.It places this invention into tested water body or atmosphere,
Under the driving of osmotic pumps 1, receives phase 21 and continuously flow through antipriming pipe 4, the pollutant in tested water body or atmosphere penetrates
The micropore of antipriming pipe 4 is received the absorption of phase 21, receives in phase coil pipe 3 and is stored in after absorbing the entrance of reception phase 21 of pollutant
This.After sampling, the reception phase 21 in rear reception phase coil pipe 3 is divided into several segments, by each section in rear reception phase coil pipe 3
Position determines that this section flows through the time of antipriming pipe 4, i.e. sampling time.The concentration of pollutant in each section is analyzed with analysis instrument, and
The time series concentration of pollutant in environment is just obtained in conjunction with each section of sampling time.
Embodiment 2
As shown in Figure 1, specific structure is same as Example 1, except that the aqueous solution that phase 21 is acid or alkali is received,
That is the present embodiment is used to detect the inorganic pollution (such as ammonia and hydrogen sulfide) in environment.
Embodiment 3
As shown in Fig. 2, the structure of the present embodiment and reception phase 21 are same as Example 1, the difference is that receiving phase 21
It is interior with spaced with the different interval substance 22 (preferred aqueous solutions) of the reception physicochemical properties of phase 21, to will before
The reception phase 21 received in phase coil pipe 2 is divided into section.Meanwhile between the rear liquid feeding end and the antipriming pipe 4 for receiving phase coil pipe 3
Equipped with a detection unit 5.It is different with the physicochemical properties of phase 21 are received to be spaced substance 22, when they flow through detection unit 5,
Different signals can be detected, the sampling time of sampler can be accurately determined according to this signal.
Preferably, the interval substance 22 is coloured aqueous solution, and the detection unit 5 is microspectrophotometer.
Preferably, the interval substance 22 is salting liquid, and the detection unit 5 is micro conductivity meter.
Embodiment 4
As shown in Fig. 2, the structure of the present embodiment and reception phase 21 are same as Example 2, the difference is that receiving phase 21
The interior interval substance 22 (preferably air) different from the physicochemical properties of phase 21 are received with spaced, will preceding connect
The reception phase 21 received in phase coil pipe 2 is divided into section.Meanwhile it being set between the rear liquid feeding end and the antipriming pipe 4 for receiving phase coil pipe 3
There is a detection unit 5.It is different with the physicochemical properties of phase 21 are received to be spaced substance 22, it, can when they flow through detection unit 5
It detects different signals, the sampling time of sampler can be accurately determined according to this signal.
Preferably, the detection unit 5 is microspectrophotometer or micro conductivity meter.
The foregoing is only a preferred embodiment of the present invention, the range that the present invention that therefore, it cannot be limited according to is implemented, i.e.,
Equivalent changes and modifications made in accordance with the scope of the invention and the contents of the specification should still be within the scope of the present invention.
Claims (7)
1. a kind of environmental contaminants time series concentration passive type sampling apparatus, it is characterised in that: including
One osmotic pumps, the seal casinghousing including an organic glass material, the seal casinghousing is interior to have a reverse osmosis membrane, by capsul
Body is divided into the output cavity for filling saturated sodium chloride solution and solid sodium chloride and one and fills distilled water and ion exchange resin
Input cavity；
The preceding reception phase coil pipe of one FEP, PTFE or stainless steel material, liquid feeding end is connected to the output cavity of osmotic pumps, interior preparatory
Store reception phase；
The rear reception phase coil pipe of one FEP, PTFE or stainless steel material, outlet end is connected to the input cavity of osmotic pumps, interior preparatory
Store distilled water；
With the antipriming pipe of a porous ceramics or plastic material, received before being connected to phase coil pipe outlet end and it is rear receive phase coil pipe into
Liquid end；
The reception received in phase coil pipe after above-mentioned is mutually divided into several segments, determines correspondence by each section of position in rear reception phase coil pipe
Section flows through the time i.e. sampling time of antipriming pipe.
2. a kind of environmental contaminants time series concentration passive type sampling apparatus as described in claim 1, it is characterised in that: institute
It states and receives the mutually aqueous solution for acid or alkali, to acquire the inorganic pollution in environment.
3. a kind of environmental contaminants time series concentration passive type sampling apparatus as claimed in claim 2, it is characterised in that: institute
It states and receives interval substance different from the physicochemical properties of phase are received with spaced in phase.
4. a kind of environmental contaminants time series concentration passive type sampling apparatus as described in claim 1, it is characterised in that: institute
Stating reception mutually is alkane or aromatic hydrocarbons, to acquire the organic pollutant in environment.
5. a kind of environmental contaminants time series concentration passive type sampling apparatus as claimed in claim 4, it is characterised in that: institute
It states and receives interval substance different from the physicochemical properties of phase are received with spaced in phase.
6. a kind of environmental contaminants time series concentration passive type as described in any claim in claim 1 to 5 samples
Device, it is characterised in that: received after described and be equipped with a detection unit between phase coil pipe liquid feeding end and the antipriming pipe, to determination
Receive mutually and be spaced the time that material stream crosses detection unit.
7. a kind of environmental contaminants time series concentration passive type sampling apparatus as claimed in claim 6, it is characterised in that: institute
Stating detection unit is micro conductivity instrument or microspectrophotometer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611037115.3A CN106769235B (en) | 2016-11-23 | 2016-11-23 | A kind of environmental contaminants time series concentration passive type sampling apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611037115.3A CN106769235B (en) | 2016-11-23 | 2016-11-23 | A kind of environmental contaminants time series concentration passive type sampling apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106769235A CN106769235A (en) | 2017-05-31 |
| CN106769235B true CN106769235B (en) | 2019-07-30 |
Family
ID=58971117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611037115.3A Active CN106769235B (en) | 2016-11-23 | 2016-11-23 | A kind of environmental contaminants time series concentration passive type sampling apparatus |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106769235B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108256197B (en) * | 2018-01-10 | 2021-10-22 | 四川大学 | Method for determining residence time of water body in energy dissipation pool |
| CN113358423B (en) * | 2021-05-20 | 2023-03-14 | 合肥学院 | Quasi-continuous environment atmospheric gas sampling device |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101532921A (en) * | 2008-03-11 | 2009-09-16 | 中国科学院生态环境研究中心 | Passive sampling device with hollow fiber membrane |
| CN102384895A (en) * | 2011-11-15 | 2012-03-21 | 中华人民共和国北京出入境检验检疫局 | Field atmosphere detection system and detection method thereof |
| CN102895887A (en) * | 2012-10-18 | 2013-01-30 | 中国科学院南京地理与湖泊研究所 | Aquatic plant grease-cellulose acetate composite semipermeable membrane type bionic passive sampling device |
| CN103033398A (en) * | 2012-12-19 | 2013-04-10 | 深圳市建筑科学研究院有限公司 | Timed passive air sampler |
| CN103384823A (en) * | 2010-12-03 | 2013-11-06 | 墨尔本大学 | Device and process for passive sampling |
| CN103398878A (en) * | 2013-08-15 | 2013-11-20 | 深圳市建筑科学研究院有限公司 | Passive air sampler |
| CN103558059A (en) * | 2013-11-04 | 2014-02-05 | 南开大学 | Time-controlled chitosan gel passive sampler aiming at heavy metal pollutants in water environment |
| CN105115788A (en) * | 2015-08-21 | 2015-12-02 | 厦门大学 | Water body pollutant time-weighted mean concentration sampling device based on osmotic pump and solid-phase extraction |
| CN105158018A (en) * | 2015-08-11 | 2015-12-16 | 中国科学院生态环境研究中心 | Semi-permeable membrane continuous sampling device for passive sampling of water body |
| CN205049379U (en) * | 2015-10-23 | 2016-02-24 | 厦门大学 | Active sample thief of quality of water parameter time series concentration based on infiltration pump |
| CN105784415A (en) * | 2016-03-08 | 2016-07-20 | 中国科学院生态环境研究中心 | Passive sampler for high-resolution determination of freely dissolved pollutant concentration of pore water |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090007699A1 (en) * | 2007-06-20 | 2009-01-08 | Dr. Hongmao Tang | Multigas Passive Sampler |
-
2016
- 2016-11-23 CN CN201611037115.3A patent/CN106769235B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101532921A (en) * | 2008-03-11 | 2009-09-16 | 中国科学院生态环境研究中心 | Passive sampling device with hollow fiber membrane |
| CN103384823A (en) * | 2010-12-03 | 2013-11-06 | 墨尔本大学 | Device and process for passive sampling |
| CN102384895A (en) * | 2011-11-15 | 2012-03-21 | 中华人民共和国北京出入境检验检疫局 | Field atmosphere detection system and detection method thereof |
| CN102895887A (en) * | 2012-10-18 | 2013-01-30 | 中国科学院南京地理与湖泊研究所 | Aquatic plant grease-cellulose acetate composite semipermeable membrane type bionic passive sampling device |
| CN103033398A (en) * | 2012-12-19 | 2013-04-10 | 深圳市建筑科学研究院有限公司 | Timed passive air sampler |
| CN103398878A (en) * | 2013-08-15 | 2013-11-20 | 深圳市建筑科学研究院有限公司 | Passive air sampler |
| CN103558059A (en) * | 2013-11-04 | 2014-02-05 | 南开大学 | Time-controlled chitosan gel passive sampler aiming at heavy metal pollutants in water environment |
| CN105158018A (en) * | 2015-08-11 | 2015-12-16 | 中国科学院生态环境研究中心 | Semi-permeable membrane continuous sampling device for passive sampling of water body |
| CN105115788A (en) * | 2015-08-21 | 2015-12-02 | 厦门大学 | Water body pollutant time-weighted mean concentration sampling device based on osmotic pump and solid-phase extraction |
| CN205049379U (en) * | 2015-10-23 | 2016-02-24 | 厦门大学 | Active sample thief of quality of water parameter time series concentration based on infiltration pump |
| CN105784415A (en) * | 2016-03-08 | 2016-07-20 | 中国科学院生态环境研究中心 | Passive sampler for high-resolution determination of freely dissolved pollutant concentration of pore water |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106769235A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tobiszewski et al. | Green analytical chemistry—theory and practice | |
| Zhang et al. | Modelling of vacuum membrane distillation | |
| Dasgupta | A diffusion scrubber for the collection of atmospheric gases | |
| EP0832436A1 (en) | Apparatus and method for analysis | |
| CN106769235B (en) | A kind of environmental contaminants time series concentration passive type sampling apparatus | |
| US6296685B1 (en) | Device and method for sampling in liquid phases using a diffusion body and an analyte-binding phase | |
| Khulu et al. | Development and application of a membrane assisted solvent extraction-molecularly imprinted polymer based passive sampler for monitoring of selected pharmaceuticals in surface water | |
| US8413490B2 (en) | Modular underwater sampling apparatus | |
| Tweedie et al. | The analysis of dissolved inorganic carbon in liquid using a microfluidic conductivity sensor with membrane separation of CO 2 | |
| Lanfranco et al. | Phantom membrane microfluidic cross-flow filtration device for the direct optical detection of water pollutants | |
| CN110133180B (en) | Substance detection system and method based on gated pressure threshold change | |
| CN103721567B (en) | A kind of sample solution purifier based on hollow fiber nanofiltration membrane material | |
| Willauer et al. | Effects of pressure on the recovery of CO2 by phase transition from a seawater system by means of multilayer gas permeable membranes | |
| CN103776879B (en) | A kind of method of molecular engram solid phase extraction technology-potentiometry combination detection organic pollution | |
| CN105115788B (en) | Water pollutant time weighted average concentration sampler based on osmotic pumps and Solid Phase Extraction | |
| CN108731963A (en) | The passive sampling apparatus and method of polarity organic pollution in rice soil | |
| Toda | Trends in atmospheric trace gas measurement instruments with membrane-based gas diffusion scrubbers | |
| Tian et al. | A permeable membrane capacitance sensor for ionogenic gases: Application to the measurement of total organic carbon | |
| Willauer et al. | Recovery of CO2 by Phase Transition from an Aqueous Bicarbonate System under Pressure by Means of Multilayer Gas Permeable Membranes | |
| Garbarini et al. | Diffusion and reverse osmosis through polymer membranes | |
| DE102014217342B4 (en) | Mobile sensor system | |
| Majeed et al. | Home-Made Micro Valve for Determining Malachite Green Dye by Flow Injection Analysis | |
| CN109613168A (en) | The method for monitoring sulfur dioxide concentration in gas attack chamber on-line | |
| Van Gauwbergen et al. | Assessment of the design parameters for wastewater treatment by reverse osmosis | |
| Sharara et al. | Development of membrane introduction mass spectrometry for monitoring trace organics in water |
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 |