CN112945692A - Bubbling separation online enrichment system for trace heavy metals in environmental water - Google Patents
Bubbling separation online enrichment system for trace heavy metals in environmental water Download PDFInfo
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- CN112945692A CN112945692A CN202110166228.8A CN202110166228A CN112945692A CN 112945692 A CN112945692 A CN 112945692A CN 202110166228 A CN202110166228 A CN 202110166228A CN 112945692 A CN112945692 A CN 112945692A
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- 238000000926 separation method Methods 0.000 title claims abstract description 49
- 230000005587 bubbling Effects 0.000 title claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 230000007613 environmental effect Effects 0.000 title claims abstract description 36
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 28
- 238000002347 injection Methods 0.000 claims abstract description 92
- 239000007924 injection Substances 0.000 claims abstract description 92
- 238000001514 detection method Methods 0.000 claims abstract description 16
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims abstract description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 10
- 238000004587 chromatography analysis Methods 0.000 claims abstract description 9
- 238000004090 dissolution Methods 0.000 claims abstract description 8
- 239000006260 foam Substances 0.000 claims abstract description 6
- 239000000523 sample Substances 0.000 claims description 76
- 239000000243 solution Substances 0.000 claims description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000005070 sampling Methods 0.000 claims description 28
- 239000002244 precipitate Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims description 21
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 11
- 239000012498 ultrapure water Substances 0.000 claims description 11
- 239000002699 waste material Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 239000012488 sample solution Substances 0.000 claims description 3
- 229960004887 ferric hydroxide Drugs 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims 1
- 238000007790 scraping Methods 0.000 abstract description 9
- 239000013049 sediment Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 230000003321 amplification Effects 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 238000001636 atomic emission spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910021655 trace metal ion Inorganic materials 0.000 description 1
Images
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
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
-
- 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
- G01N1/4055—Concentrating samples by solubility techniques
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
-
- 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
- G01N1/4055—Concentrating samples by solubility techniques
- G01N2001/4066—Concentrating samples by solubility techniques using difference of solubility between liquid and gas, e.g. bubbling, scrubbing or sparging
Abstract
The invention discloses a bubbling separation online enrichment system for trace heavy metals in environmental water, and relates to the technical field of separation and enrichment of heavy metal ions in environmental water. The system comprises a sample introduction system, a bubbling separation enrichment system and a precipitation dissolution sample introduction system. The sample injection system comprises an 8-way multi-position valve, a polytetrafluoroethylene tube and a syringe pump. The separation and enrichment system is designed into an amplification plate chromatography column shape, a half arc-shaped groove is embedded outside, and the front part scrapes the sediment carrying the foam into the arc-shaped groove through a mechanical arm by a scraping blade. The precipitation dissolution sample introduction system is used for adding acid to dissolve the precipitation in the arc-shaped groove and then detecting the precipitation on a machine. The invention realizes the linearization of the bubbling separation, thereby achieving the enrichment effect. The system has simple structure and low cost, can be used together with detection instruments such as atomic absorption instruments, ICP-OES instruments and the like, realizes on-line separation and enrichment of metal ions in the water sample, and has good use effect.
Description
Technical Field
The invention belongs to the field of online separation and enrichment, and particularly relates to an enrichment device and method for realizing the online bubbling separation method.
Background
ICP-AES analyzer (atomic emission spectrometer). The inductively coupled plasma atomic emission spectrometer is mainly used for qualitative and quantitative analysis of inorganic elements, and is used as a large-scale precise inorganic analysis instrument. The method is widely applied to rare earth analysis, noble metal analysis, alloy materials, electronic products, medical and health departments, metallurgy departments, geology departments, petroleum departments, chemical departments, commodity inspection departments, environmental protection departments and the like.
The sensitivity of the prior art (ICP-AES) to trace metals in environmental water is low, the detection limits of ICP-AES to Cd, Be, Pb, As, Cr, Cu and Sb elements in the standard HJ776-2015 are respectively 4, 0.2, 20, 35, 19, 9 and 30 mu g/L, the detection limits of Cd, Be, Pb, As, Cr, Cu and Sb in the surface water environmental quality standard GB3838-2002 are respectively 1, 2, 10, 50, 10, 10 and 5, when the metal concentration in a water sample is lower than the detection limit of the ICP-AES or is close to the detection limit of the ICP-AES, the ICP-AES can not accurately detect the concentration of the metal ions in the environmental water directly by using the ICP-AES, therefore, the invention provides an online enrichment method of trace metals in the environmental water, the water sample, a coprecipitator sodium hydroxide are mixed in a bubbling mode by a sequential injection method, the precipitation is carried to the top of the chromatographic column by attaching the precipitation by the principle of generating bubbles by a surfactant to realize online enrichment. The system has the advantages of simple structure, low cost, simple and convenient operation and better enrichment effect.
Disclosure of Invention
The present invention is directed to solving the above problems of the prior art. Provides a bubbling separation on-line enrichment system for trace heavy metals in environmental water. The technical scheme of the invention is as follows:
1. the bubble separation online enrichment system for trace heavy metals in environmental water is characterized in that sequential injection bubble separation and inductively coupled atomic body atomic emission spectroscopy are combined, and a sample solution to be detected, a coprecipitator solution and a surfactant are input into a self-made bubble separator through an injection pump conveying pipeline by adopting a sequential injection method to enrich the heavy metals. The method comprises the following steps: an online sample introduction system, a bubbling separation enrichment system and a precipitation dissolution sample introduction system. The online sample introduction system is used for determining the sample introduction sequence and the sample introduction volume of different solutions. The bubbling separation enrichment system is used for generating the precipitate on line and separating the precipitate in the form of bubbling. And a precipitate dissolving system for dissolving the precipitate and delivering the solution to the detection instrument.
Further, solution on-line sampling system includes one eight lead to multiposition valve (1), first tee bend battery valve (2), second tee bend battery valve (3), a cross valve (4), first syringe pump (5), second syringe pump (6) ambient water sampling pipeline (7), dilute nitric acid sampling pipeline (8), concentrated nitric acid sampling pipeline (9), coprecipitator iron chloride solution sampling pipeline (10), sodium hydroxide sampling pipeline (11), ultrapure water sampling pipeline (12), surfactant sampling pipeline (13), foam stabilizer (14). The second three-way battery valve (3) is respectively connected with two injection pumps with different measuring ranges, the measuring range of the first injection pump (5) can be 500mL and is used for sample injection of large volume of environmental water, and the measuring range of the second injection pump (6) can be 2mL and is used for sample injection of other small volume solutions. One end of the four-way valve (4) is connected with a waste liquid bottle (15) for discharging the cleaning waste liquid of the pipeline, and the other end is connected with a third three-way battery valve (16) and connected with a bubbling separation and enrichment system.
Furthermore, the bubbling separation and enrichment system is composed of a self-made polytetrafluoroethylene chromatography column (17) with the width of about 5cm, the height of about 25cm, a 3 # glass sieve plate (18) embedded at the bottom and an arc-shaped groove (19) embedded at the upper part and with the height of about 3cm, a solution conveyed from a flow path of the injection pump directly flows into the bottom of the chromatography column (17) through a third three-way battery valve (16), the bottom can be connected with an air compressor or a nitrogen blower (20) to blow air and control the gas flow rate through a float flowmeter (21), so that the solution in the chromatography column is uniformly mixed and generates bubbles to attach the sediment to the top of the chromatography column. The bottom of the chromatographic column is provided with an opening which is connected with a two-way battery valve (22) and can be used for discharging waste liquid.
Furthermore, deposit and dissolve sampling system includes a mechanical automation arm (23) and fourth tee bend battery valve (24), but the doctor-bar of loading polytetrafluoroethylene on the arm for from a left side to the right deposit with the bubble is scraped to arc wall (19) in, adds concentrated nitric acid through fourth tee bend battery valve (24) and dissolves the ferric hydroxide deposit and send the solution into detecting instrument.
Furthermore, the sampling pipeline is made of corrosion-resistant polytetrafluoroethylene, and the connectors are detachably connected.
Furthermore, the eight-way multi-position valve (1), the first three-way battery valve (2), the second three-way battery valve (3), the third three-way battery valve (16), the fourth three-way battery valve (24), the first injection pump (5), the second injection pump (6), the mechanical automatic arm (23) and the two-way battery valve (22) are controlled to be switched on and off by software.
An operation method of a bubbling separation online enrichment system based on trace heavy metals in the environmental water comprises the following steps:
step one, sending a sample introduction instruction: the switch is controlled by software to be opened, the eight-way multi-position valve (1), the second three-way battery valve (3) and the first injection pump (5) are started, and the ultrapure water sample injection pipeline (12) starts to inject a sample and clean the pipeline; the waste liquid filling port (15) is discharged.
And step two, starting the eight-way multi-position valve (1), the second three-way battery valve (3) and the bottom air compressor or the nitrogen blower (20), starting the flow rate of the float flowmeter to 6L/min, starting the sample introduction of the environmental water sample introduction pipeline (7) to the first injection pump (5), then opening the third three-way battery valve (16), and introducing the water sample in the first injection pump (5) into the self-made chromatographic column (17).
And step three, starting the eight-way multi-position valve (1), the first three-way battery valve (2) and the second three-way battery valve (3), starting to sample the dilute nitric acid into the second injection pump (6) through the dilute nitric acid sample injection pipeline (8), opening the third three-way battery valve (16), and enabling the dilute nitric acid in the second injection pump (6) to enter the self-made chromatographic column (17) so that the pH value of the water sample is smaller than 2.
And step four, starting the eight-way multi-position valve (1) and the second three-way battery valve (3), starting to sample the ferric chloride solution into the second injection pump (6) through the ferric chloride solution sample introduction pipeline (10), opening the third three-way battery valve (16), and allowing the ferric chloride solution in the second injection pump (6) to enter the self-made chromatographic column (17).
And step five, repeating the step one, cleaning the pipeline, starting the eight-way multi-position valve (1) and the second three-way battery valve (3), starting to sample the sodium hydroxide solution into the second injection pump (6) through the sodium hydroxide solution sampling pipeline (11), opening the third three-way battery valve (16), and enabling the sodium hydroxide solution in the second injection pump (6) to enter the self-made chromatographic column (17).
And step six, repeating the step one, cleaning the pipeline, starting the eight-way multi-position valve (1) and the second three-way battery valve (3), starting the sample injection of the surfactant solution into the second injection pump through the sample injection pipeline (13), starting the second injection pump (6), opening the third three-way battery valve (16), and enabling the surfactant solution in the second injection pump (6) to enter the self-made chromatographic column (17).
And seventhly, starting the eight-way multi-position valve (1) and the second three-way battery valve (3), starting to sample the sodium oleate solution sample injection pipeline (14) of the foam stabilizer into the second injection pump (6), opening the third three-way battery valve (16), and enabling the sodium oleate solution in the second injection pump (6) to enter the self-made chromatographic column (17).
And step eight, closing the third three-way battery valve (16), starting the mechanical automatic arm (23) 3 minutes after bubbles are generated, and scraping the sediment into the arc-shaped groove (19) by the scraping blade from left to right.
And step nine, repeating the step one, cleaning the pipeline, starting the eight-way multi-position valve (1), the first three-way battery valve (2) and the second three-way battery valve (3), feeding the concentrated nitric acid sample feeding pipeline (9) to the second injection pump (6), opening the third three-way battery valve (16) and the fourth three-way battery valve (24), feeding the concentrated nitric acid in the second injection pump (6) into the arc-shaped groove (19), and dissolving the precipitate.
And step ten, starting the eight-way multi-position valve (1) and the second three-way battery valve (3), starting the sample injection of the ultrapure water sample injection pipeline (12) to the second injection pump (6), then opening the third three-way battery valve (16) and the fourth three-way battery valve (24), and enabling the ultrapure water in the second injection pump (6) to enter an arc-shaped groove (19) to fix the volume of the sample to 5 mL.
Step eleven, closing the third three-way battery valve (16), opening the fourth three-way battery valve (24), and feeding the sample in the arc-shaped groove (19) into the AES.
The invention has the following advantages and beneficial effects:
compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
1 the bubbling separation online enrichment system for trace heavy metals in environmental water provided by the invention has the advantages that online sample injection is sequentially carried out by an online mixing system, precipitates are generated online, and the precipitates are separated online. The accuracy of each sample introduction is ensured, and the manual operation error and sample pollution caused by offline enrichment on a sample to be detected are avoided; the method avoids inaccurate test results caused by too low metal concentration of the water sample and inaccurate test results caused by too low sensitivity of a detection instrument; the solution mixing process is simple, the precipitation separation process is simple, the operation is easy, and the cost is low.
2 the bubbling separation on-line enrichment system for trace heavy metals in environmental water, provided by the invention, is characterized in that a precipitation generation and separation device is designed into a large-scale chromatographic column-shaped separator, and is used for bubbling to uniformly mix a solution and generate bubbles to bring out a precipitate, the precipitate is scraped off by an automatic mechanical arm, and the precipitate is dissolved by nitric acid. The conventional bubbling separation method needs manual scraping of precipitates, different solutions can be quantitatively removed by using a multi-position valve and an injection pump, the method is simple and easy to control, a pipeline can be cleaned by using a nitric acid aqueous solution, the pipeline does not need to be replaced, and the bubbling separation method can be used for a long time; the bubbling device generates bubbles by bubbling through a glass sieve plate, can control the generation amount of the bubbles and the optimal time of flotation by only limiting the air flow speed and the dosage of the surfactant, and has simple structure. For the enrichment of a sample with larger volume, the volume of the chromatographic column is only required to be enlarged, airflow with larger flow rate is used, and the use amount of the surfactant is properly increased, so that larger enrichment times can be obtained.
3 the bubbling separation online enrichment system for trace heavy metals in environmental water provided by the invention can realize online mixing of solutions, online generation of precipitates, online separation of precipitates and online dissolution of precipitates through control of an electromagnetic valve and a program, and can also realize online detection if connected with a detection instrument. The method can be suitable for monitoring the heavy metal with lower content in the common lakes, rivers or tap water, and has strong adaptability and easy popularization. Real-time online enrichment can ensure no pollution and no subjective error in each operation. The whole enrichment process is automatically controlled by a set program, manual intervention is not needed, and the labor cost is low.
4 at present, ICP-MS is directly used for measuring the trace metals, the sensitivity of the ICP-MS is high, and the detection limit is low, so that the current optimal method for detecting the trace metals is provided. But an ICP-MS instrument is expensive, so that an online enrichment system of trace heavy metals in environmental water is developed to be used together with detection instruments such as atomic absorption instruments and ICP-OES instruments, and the detection of trace metal ions in an online water sample can be realized.
Drawings
FIG. 1 is a schematic structural diagram of a bubbling separation online enrichment system for trace heavy metals in environmental water according to a preferred embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described in detail and clearly with reference to the accompanying drawings. The described embodiments are only some of the embodiments of the present invention.
The technical scheme for solving the technical problems is as follows:
a bubbling separation online enrichment system for trace heavy metals in environmental water combines sequential injection bubbling separation with atomic body atomic emission spectroscopy such as inductive coupling and the like, and comprises the steps of inputting a sample solution to be detected, a coprecipitator solution and a surfactant into a self-made bubbling separator through an injection pump conveying pipeline by adopting a sequential injection method, and enriching the heavy metals. The method comprises the following steps: an online sample introduction system, a bubbling separation enrichment system and a precipitation dissolution sample introduction system; the online sample introduction system is used for determining the sample introduction sequence and the sample introduction volume of different solutions. The bubbling separation enrichment system is used for generating the precipitate on line and separating the precipitate in the form of bubbling. And a precipitate dissolving system for dissolving the precipitate and delivering the solution to the detection instrument.
Preferably, the bubbling separation online enrichment system for trace heavy metals in environmental water is characterized in that the solution online sampling system comprises an eight-way multi-position valve (1), a first three-way battery valve (2), a second three-way battery valve (3), a four-way valve (4), a first injection pump (5), a second injection pump (6), an environmental water sampling pipeline (7), a dilute nitric acid sampling pipeline (8), a concentrated nitric acid sampling pipeline (9), a coprecipitator ferric chloride solution sampling pipeline (10), a sodium hydroxide sampling pipeline (11), an ultrapure water sampling pipeline (12), a surfactant sampling pipeline (13) and a foam stabilizer (14). The second three-way battery valve (3) is respectively connected with two injection pumps with different measuring ranges, the measuring range of the first injection pump (5) can be 500mL and is used for sample injection of large volume of environmental water, and the measuring range of the second injection pump (6) can be 2mL and is used for sample injection of other small volume solutions. One end of the four-way valve (4) is connected with a waste liquid bottle (15) for discharging the cleaning waste liquid of the pipeline, and the other end is connected with a third three-way battery valve (16) and connected with a bubbling separation and enrichment system.
Preferably, the bubble separation online enrichment system for trace heavy metals in environmental water is characterized in that the bubble separation enrichment system is composed of a self-made polytetrafluoroethylene chromatographic column (17) with the width of about 5cm, the height of about 25cm, a number 3 glass sieve plate (18) embedded at the bottom and an arc-shaped groove (19) embedded at the upper part and with the height of about 3cm, a solution conveyed from a flow path of an injection pump directly flows into the bottom of the chromatographic column (17) through a third three-way battery valve (16), and the bottom can be connected with an air compressor or nitrogen blower (20) to blow air and control the flow rate of the gas through a float flowmeter (21), so that the solution in the chromatographic column is uniformly mixed, bubbles are generated, and the sediment is attached to the top of the bubble upper band chromatographic column. The bottom of the chromatographic column is provided with an opening which is connected with a two-way battery valve (22) and can be used for discharging waste liquid.
Preferably, the bubbling separation online enrichment system for trace heavy metals in environmental water is characterized in that the precipitation dissolution sample injection system comprises a mechanical automatic arm (23) and a fourth three-way battery valve (24), a scraping blade capable of loading polytetrafluoroethylene is arranged on the mechanical arm and used for scraping precipitates with bubbles into an arc-shaped groove (19) from left to right, the bubbling time is constant due to constant air flow, the volume of bubbles generated within 3 minutes is constant, the volume of bubbles scraped by the scraping blade is also constant, a certain volume of concentrated nitric acid is added through the fourth three-way battery valve (24) to dissolve iron hydroxide precipitates and add ultrapure water to 5mL, and the solution is sent into a detection instrument.
Preferably, the bubbling separation online enrichment system for trace heavy metals in environmental water is characterized in that the sample introduction pipeline is made of corrosion-resistant polytetrafluoroethylene, and the connectors are detachably connected.
Preferably, the bubbling separation online enrichment system for trace heavy metals in environmental water is characterized in that the eight-way multi-position valve (1), the first three-way battery valve (2), the second three-way battery valve (3), the third three-way battery valve (16), the fourth three-way battery valve (24), the first injection pump (5), the second injection pump (6), the mechanical automatic arm (23) and the two-way battery valve (22) are controlled to be switched on and off by software.
An operation method of an online bubbling separation and enrichment system based on trace heavy metals in the environmental water comprises the following steps:
step one, sending a sample introduction instruction: the switch is controlled by software to be opened, the eight-way multi-position valve (1), the second three-way battery valve (3) and the first injection pump (5) are started, and the ultrapure water sample introduction pipeline (12) starts to introduce a sample and clean the pipeline and is discharged from the waste liquid port (15).
And step two, starting the eight-way multi-position valve (1), the second three-way battery valve (3) and the bottom air compressor or the nitrogen blower (20), starting the flow rate of the float flowmeter to 6L/min, starting the sample introduction of the environmental water sample introduction pipeline (7) to the first injection pump (5), then opening the third three-way battery valve (16), and introducing the water sample in the first injection pump (5) into the self-made chromatographic column (17).
And step three, starting the eight-way multi-position valve (1), the first three-way battery valve (2) and the second three-way battery valve (3), starting to sample the dilute nitric acid into the second injection pump (6) through the dilute nitric acid sample injection pipeline (8), opening the third three-way battery valve (16), and enabling the dilute nitric acid in the second injection pump (6) to enter the self-made chromatographic column (17) so that the pH value of the water sample is smaller than 2.
And step four, starting the eight-way multi-position valve (1) and the second three-way battery valve (3), starting to sample the ferric chloride solution into the second injection pump (6) through the ferric chloride solution sample introduction pipeline (10), opening the third three-way battery valve (16), and allowing the ferric chloride solution in the second injection pump (6) to enter the self-made chromatographic column (17).
And step five, repeating the step one, cleaning the pipeline, starting the eight-way multi-position valve (1) and the second three-way battery valve (3), starting to sample the sodium hydroxide solution into the second injection pump (6) through the sodium hydroxide solution sampling pipeline (11), opening the third three-way battery valve (16), and enabling the sodium hydroxide solution in the second injection pump (6) to enter the self-made chromatographic column (17).
And step six, repeating the step one, cleaning the pipeline, starting the eight-way multi-position valve (1) and the second three-way battery valve (3), starting the sample injection of the surfactant solution into the second injection pump through the sample injection pipeline (13), starting the second injection pump (6), opening the third three-way battery valve (16), and enabling the surfactant solution in the second injection pump (6) to enter the self-made chromatographic column (17).
And seventhly, starting the eight-way multi-position valve (1) and the second three-way battery valve (3), starting to sample the sodium oleate solution sample injection pipeline (14) of the foam stabilizer into the second injection pump (6), opening the third three-way battery valve (16), and enabling the sodium oleate solution in the second injection pump (6) to enter the self-made chromatographic column (17).
And step eight, closing the third three-way battery valve (16), starting the mechanical automatic arm (23) 3 minutes after bubbles are generated, and scraping the sediment into the arc-shaped groove (19) by the scraping blade from left to right.
And step nine, repeating the step one, cleaning the pipeline, starting the eight-way multi-position valve (1), the first three-way battery valve (2) and the second three-way battery valve (3), feeding the concentrated nitric acid sample feeding pipeline (9) to the second injection pump (6), opening the third three-way battery valve (16) and the fourth three-way battery valve (24), feeding the concentrated nitric acid in the second injection pump (6) into the arc-shaped groove (19), and dissolving the precipitate.
And step ten, starting the eight-way multi-position valve (1) and the second three-way battery valve (3), starting the sample injection of the ultrapure water sample injection pipeline (12) to the second injection pump (6), then opening the third three-way battery valve (16) and the fourth three-way battery valve (24), and enabling the ultrapure water in the second injection pump (6) to enter an arc-shaped groove (19) to fix the volume of the sample to 5 mL.
Step eleven, closing the third three-way battery valve (16), opening the fourth three-way battery valve (24), and feeding the sample in the arc-shaped groove (19) into the AES.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above examples are to be construed as merely illustrative and not limitative of the remainder of the disclosure. After reading the description of the invention, the skilled person can make various changes or modifications to the invention, and these equivalent changes and modifications also fall into the scope of the invention defined by the claims.
Claims (6)
1. The bubble separation online enrichment system for trace heavy metals in environmental water is characterized in that sequential injection bubble separation and inductively coupled plasma atomic emission spectroscopy are combined, and a sample solution to be detected, a coprecipitator solution and a surfactant are input into a self-made bubble separator through an injection pump conveying pipeline by adopting a sequential injection method to enrich the heavy metals. The method comprises the following steps: an online sample introduction system, a bubbling separation enrichment system and a precipitation dissolution sample introduction system; the online sample introduction system is used for determining the sample introduction sequence and the sample introduction volume of different solutions. The bubbling separation enrichment system is used for generating the precipitate on line and separating the precipitate in the form of bubbling. And a precipitate dissolving system for dissolving the precipitate and delivering the solution to the detection instrument.
2. The bubbling separation online enrichment system for trace heavy metals in environmental water according to claim 1, wherein the solution online sampling system comprises an eight-way multi-position valve (1), a first three-way battery valve (2), a second three-way battery valve (3), a four-way valve (4), a first injection pump (5), a second injection pump (6), an environmental water sampling pipeline (7), a dilute nitric acid sampling pipeline (8), a concentrated nitric acid sampling pipeline (9), a coprecipitator ferric chloride solution sampling pipeline (10), a sodium hydroxide sampling pipeline (11), an ultrapure water sampling pipeline (12), a surfactant sampling pipeline (13) and a foam stabilizer (14). The second three-way battery valve (3) is respectively connected with two injection pumps with different measuring ranges, the measuring range of the first injection pump (5) can be 500mL and is used for sample injection of large volume of environmental water, and the measuring range of the second injection pump (6) can be 2mL and is used for sample injection of other small volume solutions. One end of the four-way valve (4) is connected with a waste liquid bottle (15) for discharging the cleaning waste liquid of the pipeline, and the other end is connected with a third three-way battery valve (16) and connected with a bubbling separation and enrichment system.
3. The on-line bubble separation and enrichment system for trace heavy metals in environmental water as claimed in claim 2, wherein the bubble separation and enrichment system is composed of a self-made polytetrafluoroethylene chromatography column (17) with a width of about 5cm, a height of about 25cm, a bottom embedded with a No. 3 glass sieve plate (18), and an upper embedded arc-shaped groove (19) with a height of about 3cm, wherein a solution delivered from a flow path of an injection pump directly flows into the bottom of the chromatography column (17) through a third three-way battery valve (16), the bottom can be connected with an air compressor or nitrogen blower (20) for air blowing, and a float flowmeter (21) is used for controlling the flow rate of gas, so that the solution in the chromatography column is uniformly mixed, bubbles are generated, and the precipitates are attached to the top of the bubble upper band chromatography column. The bottom of the chromatographic column is provided with an opening which is connected with a two-way battery valve (22) and can be used for discharging waste liquid.
4. The bubbling separation online enrichment system for trace heavy metals in environmental water according to claim 3, wherein the precipitation dissolution sample injection system comprises a mechanical automatic arm (23) and a fourth three-way battery valve (24), a scraper of polytetrafluoroethylene can be loaded on the mechanical arm, the precipitation with bubbles is scraped into the arc-shaped groove (19) from left to right, the bubbling time is constant because the gas flow is kept constant, the volume of bubbles generated within 3 minutes is constant, the volume of bubbles scraped by the scraper is also constant, a certain volume of concentrated nitric acid is added through the fourth three-way battery valve (24) to dissolve the ferric hydroxide precipitation, and ultrapure water is added to 5mL, and the solution is sent into a detection instrument.
5. The system of claim 4, wherein the sample introduction pipeline is made of corrosion-resistant polytetrafluoroethylene, and the plurality of joints are detachably connected.
6. The bubbling separation online enrichment system for trace heavy metals in environmental water according to claim 5, wherein the eight-way multi-position valve (1), the first three-way battery valve (2), the second three-way battery valve (3), the third three-way battery valve (16), the fourth three-way battery valve (24), the first injection pump (5), the second injection pump (6), the mechanical automatic arm (23), and the two-way battery valve (22) are controlled by software to be opened and closed.
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Application publication date: 20210611 |