CN110514508B - Device and method for simply, conveniently, quickly and efficiently separating and enriching boron - Google Patents
Device and method for simply, conveniently, quickly and efficiently separating and enriching boron Download PDFInfo
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- CN110514508B CN110514508B CN201910887796.XA CN201910887796A CN110514508B CN 110514508 B CN110514508 B CN 110514508B CN 201910887796 A CN201910887796 A CN 201910887796A CN 110514508 B CN110514508 B CN 110514508B
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 37
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- 238000005485 electric heating Methods 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims description 29
- 239000003929 acidic solution Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 abstract description 12
- 230000002378 acidificating effect Effects 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 101100327917 Caenorhabditis elegans chup-1 gene Proteins 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/0011—Heating features
- B01D1/0017—Use of electrical or wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/30—Accessories for evaporators ; Constructional details thereof
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4022—Concentrating samples by thermal techniques; Phase changes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4022—Concentrating samples by thermal techniques; Phase changes
- G01N2001/4027—Concentrating samples by thermal techniques; Phase changes evaporation leaving a concentrated sample
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention provides a device and a method for simply, conveniently, quickly and efficiently separating and enriching boron, which comprises a cup-shaped body, a cover-shaped body, an electric heating plate and a temperature controller, wherein the middle part of the cover-shaped body is provided with a cylindrical inner cavity, an acidic liquid sample is placed in the cylindrical inner cavity, and the cup-shaped body and the cover-shaped body are provided with matched threads which can be completely screwed and sealed. The cup-shaped body is reversely buckled on the cylindrical inner cavity and is put into the holes of the electric heating plate together, and the temperature controller is electrically connected with a plurality of holes of the electric heating plate and is used for accurately controlling the heating temperature of each hole. And after the solution is completely evaporated and condensed in the cylindrical cavity of the cover body, extracting the solution and measuring the solution. The invention expands the application range of the natural samples, most liquid samples and digested solid samples can be used by the device, the samples can be processed in batches, the application range of the samples is expanded, and the device has larger market and application space.
Description
Technical Field
The invention belongs to the technical field of separation and purification of chemical elements, and particularly relates to a device and a method for simply, conveniently, quickly and efficiently separating and enriching boron.
Background
As shown in fig. 1, which is an existing apparatus for separating boron, boron has two stable isotopes, 10 b and 11 B. the large mass difference between the two stable isotopes causes great fractionation difference (+145%o) of the boron isotopes in nature, so that the boron isotopes are widely applied in nature. At present, MC-ICP-MS (Multi-receiving inductively coupled plasma Mass Spectrometry) is used for testing boron isotopes. The boron in the sample needs to be separated from other elements and then enriched before the sample is subjected to the boron isotope test. Most people use a method of a boron specific resin or a method of combining the boron specific resin and an anion-cation resin to separate and enrich boron, and the continuous operation time is about 9 hours.
In the solution, boron is mainlyBy H 3 BO 3 And B (OH) 4 - Both forms exist. Under acidic conditions, the boron in the solution is mainly H 3 BO 3 In the form, volatile, especially in high temperature environments. With this feature, gaillardet et al 2001 designed a device as shown in fig. 1 for separation and enrichment of boron in liquids. About 50-100. Mu.L of the acid sample was placed in the middle of a 5mL PFA cover 101, and then a cup 102 was wrapped with aluminum foil paper and placed on a flat electric plate 103 for heating. By utilizing the volatilization characteristic of boron under the acidic condition, only boron element is evaporated to the upper sharp type, and other elements remain on the cover. After the sample is evaporated, the cup is cooled in a natural state. And then taking out the liquid evaporated and condensed at the upper sharp part for testing.
Although the apparatus of fig. 1 described above allows for separation and enrichment of boron in a liquid sample, certain drawbacks exist. 1. The device can only evaporate 50-100. Mu.L of the acidic sample. Furthermore, the capacity of the upper pointed part is exceeded, so that the sample can flow back into the cover, and the separation effect is not achieved. Since the final sample boron concentration is typically required to be 100 μg/L and 3mL is required for testing, the original sample boron concentration is required to be higher than 3 μg/mL. However, the boron concentration of the natural liquid sample, mainly river water, well water and rainwater, is at ppb level, so that the device for drawing the figure cannot be widely applied, and is only suitable for high-boron concentration samples.
The device of fig. 1 requires that the lid be opened and then the sample be removed from the upper spike after the sample has evaporated and condensed, which is a difficult operation with little care and drops of liquid above it will fall.
The plane electric heating plate is heated unevenly, only the cover-shaped body can be heated, and the cup-shaped body is easy to be cooled by air, so that the temperature of the cup body is easy to change, and particularly, the evaporation temperature of all samples is difficult to be the same in middle and edge samples, and the maximum temperature can reach 5 ℃. Therefore, the evaporation and condensation time of each sample is different, so that the uniformity is difficult to realize, and the operation is inconvenient.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a device and a method for simply, conveniently, rapidly and efficiently separating and enriching boron, which can carry out sample treatment in a large scale, expand the application range of samples and have larger market and application space.
The invention adopts the following technical scheme:
the utility model provides a simple and convenient, quick, high-efficient separation enrichment boron's device, includes cup and lid to and electric plate and temperature controller, lid middle part has cylindrical inner chamber, treats the enrichment solution and arranges cylindrical inner chamber in, cup back-off, twist on the lid of taking cylindrical inner chamber, and cup oral area inserts in the cavity between lid cylindrical inner chamber and the outer fringe, constitutes heating container, puts into the downthehole of electric plate together, and the temperature controller is connected with electric plate a plurality of holes realization electricity for the heating temperature of every aperture of accurate control.
According to a further technical scheme, the maximum end diameter of the cup-shaped body and/or the maximum end diameter of the cover-shaped body are/is smaller than the inner diameter of the hole, so that the cover-shaped body and/or the cup-shaped body can be placed into the hole of the electric heating plate.
According to a further technical scheme, the cup-shaped body is buckled on the cover-shaped body, and the cup-shaped body and the cover-shaped body are provided with matched threads, so that the cup-shaped body and the cover-shaped body can be completely screwed together, and the purpose of sealing a sample to be evaporated is achieved.
The further technical proposal is that a heating container is formed, and when the heating container and the heating container are put into the holes of the electric heating plate together, the bottom of the cup-shaped body is reserved to be 0.5cm outside the holes.
The further technical proposal is that the temperature controller accurately controls the heating temperature, so that the temperature in each hole of the electric heating plate can not differ by 0.5 ℃.
The preparation process of the invention comprises the following steps:
step 1. Making a container of the collected acidic solution
The cup-shaped body with proper size is used, then the corresponding cover-shaped body is processed, the middle part of the cover-shaped body is provided with a cylindrical inner cavity, and the solution to be enriched can be put in.
Step 2, manufacturing a heating container
The cup-shaped body is reversely buckled on the cover-shaped body, is screwed up through threaded connection and is placed into the electric heating plate hole, and only 0.5cm is left outside, so that the condensation of evaporating solution and the final cup cover body taking out are facilitated.
Step 3, heating to prepare plastic solution
The temperature controller is used for precisely controlling the heating temperature. The electric heating plate is provided with holes, the cup-shaped body and the cover-shaped body can be combined and then placed in the holes, the side surfaces of the cover-shaped body and the cup-shaped body can be heated simultaneously, the temperature of each hole can be achieved by using the temperature sensor and cannot be different by 0.5 ℃, the consistency of heating temperature is achieved, when the solution to be enriched in the cylindrical inner cavity evaporates to a certain amount, the evaporated solution to be enriched can flow back into the cover-shaped body outside the cylindrical inner cavity along the wall of the cup, and after the solution to be enriched evaporates completely and is condensed, the cup-shaped body can be opened, and the phenomenon that the solution to be enriched in boron leaks does not occur.
The invention has the beneficial effects that:
the device expands the application range of boron isotope preparation, and the device can be used for separating and enriching the boron isotopes of most liquid samples and solid digested samples. The method is convenient to operate, and only needs to put a sample into the method, cover the cup-shaped body, put the cup-shaped body on an electric heating plate for heating, and then condense and take out the cup-shaped body. Sample pretreatment was not performed on a laboratory throughout the day.
At present, the electric heating plate designed by the invention can be placed into a plurality of samples at one time. Later, according to the size of laboratory bench, design bigger electric plate, cup and lid form body, put into more samples in batches.
In a word, the device of the invention saves time and labor, is convenient to operate, can process samples in a large scale, expands the application range of the samples, and has larger market and application space.
Drawings
FIG. 1 is a prior art apparatus for separating boron;
FIG. 2 is a schematic view of the cup-shaped body of the present invention;
FIG. 3 is a schematic view of the structure of the cover body of the present invention;
fig. 4 is a schematic structural view of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in fig. 2, 3 and 4, the device for separating and enriching boron simply, quickly and efficiently comprises a cup-shaped body 1, a cover-shaped body 2, an electric heating plate 3 and a temperature controller 4, wherein a cylindrical inner cavity 201 is arranged in the middle of the cover-shaped body 2, a solution to be enriched is arranged in the cylindrical inner cavity 201, the cup-shaped body is reversely buckled on the cylindrical inner cavity 201, the opening of the cup-shaped body 1 is inserted into a cavity 202 between the cylindrical inner cavity 201 and an outer edge 203 of the cover-shaped body to form a heating container, the heating container is placed into holes 30 of the electric heating plate 3 together, and the temperature controller 4 is electrically connected with a plurality of holes 30 of the electric heating plate 3 and is used for accurately controlling the heating temperature of each hole 30.
According to a further technical scheme, the maximum end diameter of the cup-shaped body 1 and/or the maximum end diameter of the cover-shaped body 2 are/is smaller than the inner diameter of the hole, so that the cover-shaped body 2 and/or the cup-shaped body 1 can be placed in the hole 30 of the electric heating plate 3.
According to the further technical scheme, the cup-shaped body 1 and the cover-shaped body 2 are provided with matched threads, and can be screwed together to achieve a sealing effect.
Further technical proposal is that when the heating container is formed and put into the hole 30 of the electric heating plate 3 together, the bottom of the cup-shaped body 1 is reserved to be 0.5cm outside the hole 30.
Further technical proposal is that the temperature controller 4 precisely controls the heating temperature so that the temperature in each hole 30 of the electric heating plate 3 will not differ by 0.5 ℃.
The preparation process of the invention comprises the following steps:
step 1. Making a container of the collected acidic solution
In order to increase the evaporation of the sample, a cup 1 of suitable size is used, although a cup 1 of larger volume may be used as desired. Then the corresponding cover-shaped body 2 is processed, the inner middle part of the cover-shaped body 2 is provided with a cylindrical inner cavity 201, and the solution to be enriched can be put in.
Step 2, manufacturing a heating container
The cover-shaped body 2 is placed into the holes 30 of the electric heating plate 3 and is buckled by the cup-shaped body 1, the port of the cup-shaped body 1 is inserted into the cavity 202 between the cylindrical cavity 201 and the outer edge 203 of the cover-shaped body, the cup-shaped body 1 and the cover-shaped body 2 are both provided with threads, the outer edge (non-cylindrical cavity 201) of the cover-shaped body 2 and the outer edge 203 of the port of the cup-shaped body 1 can be completely screwed together to play a role in sealing, or the outer edge 203 of the mouth of the cup-shaped body 1 is provided with external threads, the inner wall of the outer edge 203 of the cover-shaped body 2 is provided with internal threads, the cup-shaped body 1/cover-shaped body 2 can be completely placed into each hole 30 of the electric heating plate 3, and only 0.5cm of the bottom of the cup-shaped body 1 is reserved outside the holes 30, so that the condensation of an evaporating solution and the final device can be conveniently taken out.
Step 3, heating to prepare plastic solution
The temperature controller 4 is used for accurately controlling the heating temperature, the electric heating plate 3 is provided with holes, the cup-shaped body 1 and the cover-shaped body 2 are combined and then are simultaneously placed in the holes 30, the cover-shaped body 2 and the cup-shaped body 1 can be heated simultaneously, the temperature in each hole 30 cannot be different by 0.5 ℃, the consistency of the heating temperature is achieved, when the solution to be enriched in the cylindrical inner cavity 201 of the cover-shaped body 2 is evaporated to a certain amount, the evaporated solution to be enriched can flow back into the cover-shaped body 2 outside the cylindrical inner cavity 201 along the wall of the cup, and after the solution to be enriched is evaporated completely and condensed, the cup-shaped body 1 can be opened, and the phenomenon that the solution to be enriched leaks can not occur.
Examples
Experiments have shown that 3mL of acid sample, using a 15mL PFA cup, can of course continue to use larger volumes as needed. Then, a corresponding cap 2 was processed, the inner middle part of the cap 2 had a cylindrical cavity 201, and 3mL of the liquid acidic sample was put in.
As shown in fig. 3, the cover 2 was put into the holes 30 provided in the electric heating plate 3 and was buckled by a cup, which could be put completely into each hole 30 of the electric heating plate 3, leaving only 0.5cm outside.
The temperature controller 4 is used for accurately controlling the heating temperature, the electric heating plate 3 is provided with holes, the cup-shaped body 1 and the cover-shaped body 2 are combined and then placed into the holes 30, the fact that the cover-shaped body 2 and the cup-shaped body 1 can be heated simultaneously is guaranteed, the temperature in each hole 30 cannot differ by 0.5 ℃, the consistency of the heating temperature is achieved, when the liquid acidic solution in the cylindrical inner cavity 201 evaporates to a certain amount, the evaporated liquid acidic solution can flow back into the cover (the cavity 202 between the cylindrical inner cavity 201 and the outer edge 203) along the wall of the cup, and after the acidic solution evaporates completely and is condensed, the cup can be opened, and the phenomenon that the acidic solution leaks out cannot occur.
At 90 ℃, the evaporation can be completed in 18 hours. Typically, the acidic liquid sample is placed into the device of the present invention the day afternoon and removed the next day after the night. The resin is not needed to stay in the laboratory continuously like a boron-specific resin column. In order to save time, the temperature of the electric plate 3 can be raised to 110 ℃, and 3mL of sample can be evaporated after 4 hours. Time and labor are saved, and the operation is convenient.
Compared with the background art, the invention processes a larger cylindrical inner cavity 201, and can put a larger amount of sample to be enriched. After evaporation of the enriched sample, the sample is not hung at the upper tip as shown in fig. 1, but is refluxed into the cover-like body 2 as shown in fig. 2, and there is no fear of dropping the sample due to improper operation.
And the electric heating plate 3 is provided with a hole into which the cup-shaped body 1 shown in fig. 2 can be put, the cover-shaped body 2 and the cup-shaped body 1 can be heated simultaneously (when the traditional plane electric heating plate 103 is used, only the cover-shaped body 2 can be heated, and the cup-shaped body 1 is easy to be subjected to the cooling effect of air, so that the temperature of the cup body is easy to change), the heating is more uniform, and the temperature of each sample can not be different by 0.5 ℃.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (4)
1. The device is characterized by comprising a cup-shaped body, a cover-shaped body, an electric heating plate and a temperature controller, wherein a cylindrical inner cavity is formed in the middle of the cover-shaped body, a solution to be enriched is placed in the cylindrical inner cavity, the cup-shaped body is reversely buckled on the cover-shaped body, the opening of the cup-shaped body is inserted into a cavity between the cylindrical inner cavity and the outer edge of the cover-shaped body to form a heating container, the heating container and the heating container are placed in holes of the electric heating plate together, and the temperature controller is electrically connected with a plurality of holes of the electric heating plate and is used for accurately controlling the heating temperature of each hole;
the maximum end diameter of the cup-shaped body and/or the maximum end diameter of the cover-shaped body are/is smaller than the inner diameter of the hole, so that the cover-shaped body and/or the cup-shaped body can be placed into the hole of the electric heating plate;
the cup-shaped body and the cover-shaped body are both provided with threads, and the cup-shaped body is buckled on the cover-shaped body and is sealed by screwing through the threads.
2. The apparatus for separating enriched boron simply, quickly and efficiently according to claim 1, wherein the bottom of the retaining cup is 0.5cm outside the hole when the heating container is put together in the hole of the electric hot plate.
3. The apparatus for separating enriched boron simply, quickly and efficiently according to claim 1, wherein the temperature controller precisely controls the heating temperature so that the temperature in each hole of the electric heating plate is not different by 0.5 ℃.
4. The device for separating and enriching boron simply, quickly and efficiently according to claim 1, wherein the preparation process comprises the following steps:
step 1. Making a container of the collected acidic solution
Using a cup-shaped body with proper size, then processing a corresponding cover-shaped body, wherein the middle part of the cover-shaped body is provided with a cylindrical inner cavity, and putting boron solution to be enriched;
step 2, preparing a heating container
The cup-shaped body is reversely buckled on the cover-shaped body and is screwed tightly through threads and is put into a hole of the electric heating plate, the cup-shaped body or/and the cover-shaped body can be put into any hole of the electric heating plate, and the bottom of the cup-shaped body is reserved to be 0.5cm outside the hole;
step 3, heating to prepare plastic solution
The temperature controller is used for accurately controlling the heating temperature, so that the temperature in each hole cannot differ by 0.5 ℃, the heating temperature is consistent, when the solution to be enriched in the cylindrical inner cavity evaporates to a certain amount, the evaporated solution to be enriched flows back into the cavity between the cylindrical inner cavity and the outer edge of the cover-shaped body along the inner wall of the cup-shaped body, and after the solution to be enriched evaporates completely and condenses, the cup-shaped body can be opened to obtain the boron solution to be enriched.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910887796.XA CN110514508B (en) | 2019-09-19 | 2019-09-19 | Device and method for simply, conveniently, quickly and efficiently separating and enriching boron |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910887796.XA CN110514508B (en) | 2019-09-19 | 2019-09-19 | Device and method for simply, conveniently, quickly and efficiently separating and enriching boron |
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| Publication Number | Publication Date |
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| CN110514508A CN110514508A (en) | 2019-11-29 |
| CN110514508B true CN110514508B (en) | 2023-12-29 |
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| CN210571663U (en) * | 2019-09-19 | 2020-05-19 | 中国科学院地球环境研究所 | Simple, convenient, quick, high-efficient separation enrichment boron's device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9470612B2 (en) * | 2011-06-30 | 2016-10-18 | 3M Innovative Properties Company | Systems and methods for detecting an analyte of interest in a sample using filters and microstructured surfaces |
-
2019
- 2019-09-19 CN CN201910887796.XA patent/CN110514508B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB890925A (en) * | 1959-11-20 | 1962-03-07 | Tack Air Conditioning Ltd | Improvements relating to vaporising devices |
| CN102378641A (en) * | 2009-03-31 | 2012-03-14 | 吉纳瓦克有限公司 | Method and sample holding assembly for use in sample preparation |
| CN104729906A (en) * | 2015-04-14 | 2015-06-24 | 中国科学院地球环境研究所 | Efficient and pollution-free boron isotope pressurization separating device for low-boron environmental samples |
| CN104964941A (en) * | 2015-06-29 | 2015-10-07 | 浙江大学 | Method and separating and collecting device for detecting elemental selenium quickly and quantitatively |
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| CN110514508A (en) | 2019-11-29 |
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