CN106442002B - Water sample collection device - Google Patents
Water sample collection device Download PDFInfo
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- CN106442002B CN106442002B CN201610594458.3A CN201610594458A CN106442002B CN 106442002 B CN106442002 B CN 106442002B CN 201610594458 A CN201610594458 A CN 201610594458A CN 106442002 B CN106442002 B CN 106442002B
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- 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
- G01N1/14—Suction devices, e.g. pumps; Ejector devices
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- 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
- G01N1/18—Devices for withdrawing samples in the liquid or fluent state with provision for splitting samples into portions
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
Abstract
A water sample collection device comprising: the liquid level detection device comprises a certain amount sampling module, a liquid level detection module, a bottle separating module and a sample storage module, wherein an automatic dosing module is arranged between the liquid level detection module and the bottle separating module, the dosing module comprises a reagent and a reagent quantifying module which are connected with each other, and an online liquid mixing module which is connected with the reagent quantifying module and an output end pipeline of the liquid level detection module so as to realize dosing. The online liquid mixing module is a tee joint and is respectively connected with the reagent quantifying module, the liquid level detecting module and the split screen module, one end of the online liquid mixing module is filled with a water sample, the other end of the online liquid mixing module is filled with a reagent, and the online liquid mixing module and the reagent are mixed and then are conveyed to the split bottle module through the other outlet of the tee joint.
Description
Technical Field
The invention relates to an environment-friendly and efficient water sample collection device, and belongs to the technical field of environment protection devices.
Background
The automatic water sampling device can realize automatic water sample collection and automatic preservation. The existing automatic water quality sampling devices at home and abroad at present adopt a refrigeration preservation technology on the automatic preservation of samples, and the preservation technology can inhibit chemical reaction and biological activity of water samples in the preservation process to a certain extent, but still can not meet the requirement of long-term preservation of the water samples. According to the requirements of the preservation and management technical regulations of the water quality samples of HJ493-2009 and the conventional manual sampling, the preservation of the water quality samples needs to be added with a preservative so as to meet the requirement of long-time preservation of the water quality samples, and the representativeness of water samples is fully ensured in the actual water quality sample analysis process.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an environment-friendly and efficient water sample collecting device.
The technical scheme of the invention is as follows: a water sample collection device comprising:
the quantitative sampling module is used for quantitatively sampling by a quantitative peristaltic pump, and the quantitative peristaltic pump is connected with the sample inlet;
the liquid level detection module is arranged on the water sample pipeline and connected with the quantitative sampling module, and is used for detecting whether water flows through the pipeline or not so as to eliminate the influence of the length of the front water sample pipeline on the quantitative sample;
the bottle separating module comprises a sampling and distributing arm connected with the liquid level detecting module through a pipeline, a motor for driving the distributing arm to rotate to realize the selection of the sample storage bottle number, and a photoelectric switch for detecting the position of the distributing arm to realize the accurate positioning of the distributing arm;
the sample storage module is connected with the bottle separating module and consists of a refrigerator body, a group of sampling bottles and a sampling bottle tray, wherein the group of sampling bottles and the sampling bottle tray are placed in the refrigerator body, and each sampling bottle is arranged along the rotating path of the distribution arm so as to realize sample collection;
the automatic dosing module is arranged between the liquid level detection module and the bottle distribution module, and comprises a reagent and a reagent quantifying module which are connected with each other, and an online liquid mixing module which is connected with the reagent quantifying module and an output end pipeline of the liquid level detection module so as to realize dosing.
The reagent quantitative module is a dosing diaphragm pump, a plunger pump, an injection pump or a peristaltic pump.
The online liquid mixing module is a tee joint and is respectively connected with the reagent quantifying module, the liquid level detecting module and the split screen module, one end of the online liquid mixing module is filled with a water sample, the other end of the online liquid mixing module is filled with a reagent, and the online liquid mixing module and the reagent are mixed and then are conveyed to the split bottle module through the other outlet of the tee joint.
The reagent is sulfuric acid, nitric acid, hydrochloric acid or sodium hydroxide solution.
The addition amount of sulfuric acid is controlled to be less than 2 in pH value of the sample.
When the added reagent is sulfuric acid, the system calculates the addition amount of sulfuric acid by adopting the following algorithm:
in the strong acid aqueous solution system, the formula is adopted
Calculating the addition amount of sulfuric acid;
in the strong alkaline aqueous system, the formula is adopted
Calculating the addition amount of sulfuric acid;
in a strong electrolyte neutral aqueous solution system,
using the formulaCalculating the addition amount of sulfuric acid;
in a unitary weak acid system, a formula is adopted Calculating the addition amount of sulfuric acid;
in a binary weak acid system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in the ternary weak acid system, the formula is adopted
Calculating the addition amount of sulfuric acid;
in the strong acid weak base salt water solution system, the formula is adopted
Calculating the addition amount of sulfuric acid;
in a weak base and weak base root ion aqueous solution system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in a strong base weak acid (unitary) salt system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in a strong base weak acid (binary) salt system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in a strong base weak acid (ternary) salt system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in the above-mentioned formulae of the various formulae,
pH1: pH after addition of acid;
pH0: the pH value before adding acid;
【H 2 SO 4 】 adding ：H 2 SO 4 The addition amount of (2) mol/L;
HA: unitary weak acid
A - : a first partMeta weak acid root ion;
H 2 a: binary weak acids;
HA - : binary weak acid first-stage dissociation weak acid root ion;
A 2- : binary weak acid secondary dissociation weak acid root ions;
H 3 a: ternary weak acids;
H 2 A - : primary dissociation of weak acid root ions by ternary weak acid;
HA 2- : ternary weak acid secondary dissociation weak acid root ion;
A 3- : ternary weak acid secondary dissociation weak acid root ion;
BOH: a monobasic weak base;
B + : monobasic weak base root ion;
【】 0 : initial molar concentration of the substance, mol/L;
k equilibrium constant of the substance.
When H is determined according to the above method 2 SO 4 The addition amount of [ H ] 2 SO 4 】 Adding After that, the volume ratio of sulfuric acid addition can be calculated according to the following formula:
wherein:
x: ratio of dosing volumes (ratio of reagent volume to water sample volume)
Concentrated H 2 SO 4 98g/mol;
concentrated H 2 SO 4 Density of 1.84g/ml;
【H 2 SO 4 】 adding : concentration of sulfuric acidDegree (based on the volume of the solution after adding sulfuric acid, the change of the volume of the solution before and after adding the chemical can be ignored because the chemical adding proportion is less than 1 percent), mol/L
V1: the sampler samples the volume of the added concentrated sulfuric acid for a single time;
v2: the sampler samples the total volume of the collected water sample once;
the above can be reduced to:
when the added reagent is nitric acid, hydrochloric acid, sodium hydroxide or other reagents, the system calculates the adding amount according to a fixed adding proportion X: x=v1/V2, wherein: v1 is the volume of the reagent, V2 is the volume of the sample, and X is the dosing proportion;
when the dosing proportion X is determined, the system can add the used reagent into the sample pipeline according to two modes of proportional dosing or unequal proportion dosing:
a) Mode of proportional dosing:
the required sample dosing proportion is realized by adjusting the reagent quantitative extraction flow Q1 and the water sample quantitative extraction flow Q2, and the Q1 and the Q2 satisfy the following relations:
wherein:
q1: the extraction flow rate of the reagent;
q2: extracting flow of a water sample;
b) Non-proportional dosing mode:
the required sample dosing proportion is realized by adjusting the reagent extraction flow Q1 and the water sample extraction flow Q2, and the Q1 and the Q2 satisfy the following relation:
wherein:
q1: the extraction flow rate of the reagent;
q2: extracting flow of a water sample;
the beneficial effects of the invention are as follows: the ratio of the required added reagent can be automatically calculated according to the type of the sample system, the initial solution composition and the target pH value or the dosing ratio of the sample to be controlled; after the reagent adding proportion is obtained, automatically adjusting the flow of quantitative water sample collection and the flow of quantitative reagent extraction, and automatically mixing the reagent and the sample according to the proportion so as to meet the requirement of long-time preservation of the water quality sample, and fully ensuring the representativeness of the water sample in the actual water quality sample analysis process.
Drawings
Fig. 1 is a schematic diagram of the structure of the present invention.
FIG. 2 is a block diagram of a bottle dispensing module and a sample preservation module according to the present invention.
Fig. 3 is a view from another perspective of fig. 2.
Detailed Description
As shown in fig. 1 to 3, a water sample collection device according to this embodiment includes:
the quantitative sampling module 1 is used for quantitatively sampling by a quantitative peristaltic pump, and the quantitative peristaltic pump is connected with a sample inlet and can accurately and stably extract a water sample from the sample inlet to the bottle separating module according to a set flow;
the liquid level detection module 2 is arranged on the water sample sampling pipeline and connected with the quantitative sampling module, and is used for detecting whether water flows through the pipeline or not, and the judgment condition is used as an initial condition for quantitative sampling by the automatic water quality sampling device, so that the influence of the length of the front sampling pipeline on sample quantification can be effectively eliminated;
the bottle separating module 3 comprises a sampling and distributing arm 3-2 connected with the liquid level detecting module through a pipeline, a motor 3-1 for driving the distributing arm to rotate to realize the selection of sample storage bottle numbers, and a photoelectric switch for detecting the position of the distributing arm to realize the accurate positioning of the distributing arm;
the sample preservation module 4 is connected with the bottle separation module and consists of a refrigerator body 4-1, a group of sampling bottles 4-2 and a sampling bottle tray 4-3 which are placed in the refrigerator body, wherein each sampling bottle 4-2 is arranged along the rotating path of the distribution arm 3-2 so as to realize sample collection, and meanwhile, the refrigerator body 4-1 is utilized to realize the cold preservation of samples;
an automatic dosing module is arranged between the liquid level detection module 2 and the bottle separating module 3, and comprises a reagent 5 and a reagent quantifying module 6 which are connected with each other, and an online liquid mixing module 7 which is connected with the reagent quantifying module 6 and an output end pipeline of the liquid level detection module 2 so as to realize dosing; the reagent dosing module 6 described in this example is a dosing diaphragm pump, but may also be a plunger pump, syringe pump or peristaltic pump.
The reagent is sulfuric acid (sampling analysis is carried out on indexes such as ammonia nitrogen, COD, total phosphorus, total nitrogen and the like), nitric acid (sampling analysis is carried out on indexes such as heavy metals except mercury) or hydrochloric acid (sampling analysis is carried out on mercury); wherein, the water sample preservation can be added according to a fixed proportion for adding nitric acid, hydrochloric acid and the like; the requirement for the amount of sulfuric acid added is to control the pH of the sample to < 2, so the amount of sulfuric acid reagent added to the sample needs to be determined.
When the added reagent is sulfuric acid, the system calculates the addition amount of sulfuric acid by adopting the following algorithm:
in the strong acid aqueous solution system, the formula is adopted
Calculating the addition amount of sulfuric acid;
in the strong alkaline aqueous system, the formula is adopted
Calculating the addition amount of sulfuric acid;
in a strong electrolyte neutral aqueous solution system,
using the formulaCalculating the addition amount of sulfuric acid;
in a unitary weak acid system, a formula is adopted Calculating the addition amount of sulfuric acid;
in a binary weak acid system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in the ternary weak acid system, the formula is adopted
Calculating the addition amount of sulfuric acid;
in the strong acid weak base salt water solution system, the formula is adopted
Calculating the addition amount of sulfuric acid;
in a weak base and weak base root ion aqueous solution system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in a strong base weak acid (unitary) salt system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in a strong base weak acid (binary) salt system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in a strong base weak acid (ternary) salt system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in the above-mentioned formulae of the various formulae,
pH1: pH after addition of acid;
pH0: the pH value before adding acid;
【H 2 SO 4 】 adding ：H 2 SO 4 An added amount of (2);
HA: unitary weak acid
A - : a monobasic weak acid radical ion;
H 2 a: binary weak acids;
HA - : binary weak acid first-stage dissociation weak acid root ion;
A 2- : binary weak acid secondary dissociation weak acid root ions;
H 3 a: ternary weak acids;
H 2 A - : primary dissociation of weak acid root ions by ternary weak acid;
HA 2- : ternary weak acid secondary dissociation weak acid root ion;
A 3- : ternary weak acid secondary dissociation weak acid root ion;
BOH: a monobasic weak base;
B + : monobasic weak base root ion;
【】 0 : initial of the substanceMolar concentration, mol/L
K equilibrium constant of the substance
When H is determined according to the above method 2 SO 4 The addition amount of [ H ] 2 SO 4 】 Adding After that, the volume ratio of sulfuric acid addition can be calculated according to the following formula:
wherein:
x: ratio of dosing volumes (ratio of reagent volume to water sample volume)
Concentrated H 2 SO 4 98g/mol;
concentrated H 2 SO 4 Density of 1.84g/ml;
【H 2 SO 4 】 adding : the addition concentration of sulfuric acid (based on the volume of the solution after sulfuric acid addition, the change of the volume of the solution before and after chemical addition can be ignored because the chemical addition proportion is less than 1 percent, mol/L)
V1: the sampler samples the volume of the added concentrated sulfuric acid for a single time;
v2: the sampler samples the total volume of the collected water sample once;
the above can be reduced to:
when the added reagent is nitric acid, hydrochloric acid, sodium hydroxide or other reagents, the system calculates the adding amount according to a fixed adding proportion X: x=v1/V2, wherein: v1 is the volume of the reagent added, V2 is the sample volume, and X is the dosing proportion.
After the dosing proportion X is determined, the system can add the used reagents to the sample line in two ways of proportional mixing or unequal mixing:
a) Proportional mixing mode:
the required sample dosing proportion is realized by adjusting the reagent quantitative extraction flow Q1 and the water sample quantitative extraction flow Q2, and the Q1 and the Q2 satisfy the following relations:
wherein:
q1: the extraction flow rate of the reagent;
q2: extracting flow of a water sample;
b) Non-proportional mixing mode:
the required sample dosing proportion is realized by adjusting the reagent extraction flow Q1 and the water sample extraction flow Q2, and the Q1 and the Q2 satisfy the following relation:
wherein:
q1: the extraction flow rate of the reagent;
q2: extracting flow of a water sample;
example 1: automatic sampling of water quality of automatic concentrated sulfuric acid preservative
A. Cleaning a water taking pipeline: extracting a water sample from the sample inlet through the quantitative sampling module, stopping extracting the water sample and reversely emptying the water sample to the sample inlet when the liquid level detection device detects a water level signal; the sampling pipeline is cleaned after being circulated for a plurality of times;
B. the bottle separating module selects sampling bottle numbers: according to the sampling set bottle numbers, the bottle dividing module precisely positions and drives the distribution arm to select the corresponding sampling bottle numbers through the stepping motor;
C. pre-pumping a water sample: extracting a water sample from the sample inlet through the quantitative sampling module, and stopping extracting the water sample when the liquid level detection device detects a water level signal;
D. calculating the proportion of the dosing agent: by passing throughThe type and the composition of the input solution system are used for automatically calculating the required dosing proportion. The aqueous solution system of sodium acetate is composed of AC - 、HAC、OH - 、Na + The composition of the solution is as follows:
【AC - 】＝0.1mol/L
【HAC】＝5.71*10 -3 mol/L
pH＝8
then:
【A】 0 ＝【AC - 】+【HAC】＝(1+5.71*10 -3 )mol/L
the physical property data related to the examination can be known:
K HAC ＝1.75*10 -5
K AC -＝5.71*10 -10
if the target pH value of the solution is adjusted to be 1.8, the formula is as follows:
E. on-line mixing and dosing: and according to the dosing proportion, the quantitative sampling module and the reagent quantitative module automatically adjust the extraction flow, and according to the set proportion, the on-line liquid mixing module is used for mixing the reagent and the sample and conveying the mixture to the bottle separating module and further conveying the mixture to the sample storage module. The embodiment adopts a proportional on-line mixing and dosing mode:
according to the formula:
setting the water sampling flow rate q2=1l/min, the sulfuric acid addition flow rate Q1 should be adjusted to 6ml/min.
F. And (3) emptying a sampling pipeline: and after the water sample collection is finished, the quantitative sampling module performs reverse emptying on the sampling pipeline.
Example 2: automatic sampling of water quality of automatic concentrated nitric acid preservative
A. Cleaning a water taking pipeline: extracting a water sample from the sample inlet through the quantitative sampling module, stopping extracting the water sample and reversely emptying the water sample to the sample inlet when the liquid level detection device detects a water level signal; the sampling pipeline is cleaned after being circulated for a plurality of times;
B. the bottle separating module selects sampling bottle numbers: according to the sampling set bottle numbers, the bottle dividing module precisely positions and drives the distribution arm to select the corresponding sampling bottle numbers through the stepping motor;
C. pre-pumping a water sample: extracting a water sample from the sample inlet through the quantitative sampling module, and stopping extracting the water sample when the liquid level detection device detects a water level signal;
D. setting a fixed dosing agent ratio x=0.01;
E. on-line mixing and dosing: and according to the dosing proportion, the quantitative sampling module and the reagent quantitative module automatically adjust the extraction flow, and according to the set proportion, the on-line liquid mixing module is used for mixing the reagent and the sample and conveying the mixture to the bottle separating module and further conveying the mixture to the sample storage module. The embodiment adopts a proportional on-line mixing and dosing mode:
according to the formula:
setting the water sampling flow rate q2=1l/min, the concentrated nitric acid addition flow rate Q1 should be adjusted to 1ml/min.
F. And (3) emptying a sampling pipeline: and after the water sample collection is finished, the quantitative sampling module performs reverse emptying on the sampling pipeline.
Claims (7)
1. A water sample collection device comprising:
the quantitative sampling module is used for quantitatively sampling by a quantitative peristaltic pump, and the quantitative peristaltic pump is connected with the sample inlet;
the liquid level detection module is arranged on the water sample pipeline and connected with the quantitative sampling module, and is used for detecting whether water flows through the pipeline or not so as to eliminate the influence of the length of the front water sample pipeline on the quantitative sample;
the bottle separating module comprises a sampling and distributing arm connected with the liquid level detecting module through a pipeline, a motor for driving the distributing arm to rotate to realize the selection of the sample storage bottle number, and a photoelectric switch for detecting the position of the distributing arm to realize the accurate positioning of the distributing arm;
the sample storage module is connected with the bottle separating module and consists of a refrigerator body, a group of sampling bottles and a sampling bottle tray, wherein the group of sampling bottles and the sampling bottle tray are placed in the refrigerator body, and each sampling bottle is arranged along the rotating path of the distribution arm so as to realize sample collection;
the method is characterized in that: an automatic dosing module is arranged between the liquid level detection module and the bottle distribution module, and comprises a reagent and a reagent quantifying module which are connected with each other, and an online liquid mixing module which is connected with the reagent quantifying module and an output end pipeline of the liquid level detection module so as to realize dosing;
when the added reagent is sulfuric acid, the system calculates the sulfuric acid addition in the following manner:
in the strong acid aqueous solution system, the formula is adopted
Calculating the addition amount of sulfuric acid;
in the strong alkaline aqueous system, the formula is adopted
Calculating the addition amount of sulfuric acid;
in a strong electrolyte neutral aqueous solution system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in a unitary weak acid system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in a binary weak acid system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in the ternary weak acid system, the formula is adopted
Calculating the addition amount of sulfuric acid;
in the strong acid weak base salt water solution system, the formula is adopted
Calculating the addition amount of sulfuric acid;
in a weak base and weak base root ion aqueous solution system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in a strong base weak acid (unitary) salt system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in a strong base weak acid (binary) salt system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in a strong base weak acid (ternary) salt system, a formula is adopted
Calculating the addition amount of sulfuric acid;
in the above-mentioned formulae of the various formulae,
pH1: pH after addition of acid;
pH0: the pH value before adding acid;
【H 2 SO 4 】 adding ：H 2 SO 4 The addition amount of (2) mol/L;
HA: unitary weak acid
A-: a monobasic weak acid radical ion;
H 2 a: binary weak acids;
HA-: binary weak acid first-stage dissociation weak acid root ion;
A 2- : binary weak acid secondary dissociation weak acid root ions;
H 3 a: ternary weak acids;
H 2 A - : primary dissociation of weak acid root ions by ternary weak acid;
HA 2- : ternary weak acid secondary dissociation weak acid root ion;
A 3- : ternary weak acid secondary dissociation weak acid root ion;
BOH: a monobasic weak base;
B + : monobasic weak base root ion;
【】 0 : initial molar concentration of the substance, mol/L;
k: equilibrium constant of the material.
2. The water sample collection device of claim 1, wherein the reagent dosing module is a dosing diaphragm pump, a plunger pump, a syringe pump, or a peristaltic pump.
3. The water sample collection device according to claim 1, wherein the on-line liquid mixing module is a tee joint and is respectively connected with the reagent quantifying module, the liquid level detecting module and the bottle dividing module.
4. The water sample collecting device according to claim 1, wherein the reagent is sulfuric acid, nitric acid, hydrochloric acid or sodium hydroxide solution.
5. A water sample collecting device according to claim 4, wherein the sulfuric acid is added in an amount to control the pH of the sample to be less than 2.
6. A water sample collection device according to claim 5 wherein when the reagent is sulfuric acid, the volume ratio X of sulfuric acid reagent is calculated as:
wherein:
v1: the sampler samples the volume of the added concentrated sulfuric acid for a single time;
v2: the sampler samples the total volume of the collected water sample once.
7. A water sample collection device according to claim 2 wherein the mixing of the reagent with the water sample is in a mixed mode or a non-mixed mode.
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| CN108107025A (en) * | 2017-11-24 | 2018-06-01 | 中国科学院苏州生物医学工程技术研究所 | A kind of water quality detection method and system |
| CN108226076A (en) * | 2017-12-30 | 2018-06-29 | 北方工业大学 | Miniature trace water quality on-line monitoring appearance |
| CN108303289A (en) * | 2018-03-05 | 2018-07-20 | 杭州微智兆智能科技有限公司 | Long-range water quality sampling Quality Control instrument |
| CN109612784A (en) * | 2019-01-21 | 2019-04-12 | 河海大学 | The novel equal periods rain collection device of one kind and its acquisition method |
| CN113031043A (en) * | 2020-06-10 | 2021-06-25 | 自然资源部第三海洋研究所 | Automatic distillation sample adding system and method for pre-treatment of tritium in water during measurement |
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