CN102221540A - Method and device for analyzing trace gaseous elemental mercury - Google Patents
Method and device for analyzing trace gaseous elemental mercury Download PDFInfo
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- CN102221540A CN102221540A CN2010101493722A CN201010149372A CN102221540A CN 102221540 A CN102221540 A CN 102221540A CN 2010101493722 A CN2010101493722 A CN 2010101493722A CN 201010149372 A CN201010149372 A CN 201010149372A CN 102221540 A CN102221540 A CN 102221540A
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Abstract
The invention discloses a method and a device for analyzing trace gaseous elemental mercury, and belongs to the technical field of atmospheric environment monitoring. In the method, the whole analysis process is controlled by a programmable logic controller. The method comprises the following steps of: arranging a mercury trapping tube collecting atmospheric gaseous elemental mercury (GEM) samples into a pyrolysis releaser for rapid heating, removing acid components carried by released HgO vapor from the released HgO vapor, introducing the HgO vapor into a secondary enrichment/pyrolysis releaser, and secondarily absorbing the HgO vapor by using the mercury trapping tube in the secondary enrichment/pyrolysis releaser; and rapidly heating the secondary enrichment/pyrolysis releaser, and blowing the secondarily pyrolyzed desorbed HgO vapor into a cold atomic fluorescence detector for quantitative detection by using a carrier gas. The device provided by the invention has a simple system, and is reliable in running; the atmospheric GEM samples collected by the mercury trapping tube are analyzed after being secondarily enriched, pyrolyzed and released so as to effectively reduce the limit of detection of the device and meet the requirements of trace analysis on the atmospheric GEM.
Description
Technical field
The invention belongs to the atmosphere environment supervision technical field, is a kind of trace form mercury in the atmosphere to be made up the method and apparatus of sampling.
Background technology
Mercury (Hg) is a kind of highly toxic, interior nonessential heavy metal element of biosome, also is unique heavy metal contaminants that mainly is present in atmosphere with gaseous form.Atmospheric environment is the important place that the mercury migration transforms, and the mercury in the atmospheric environment mainly is divided into according to the physical chemistry form: gaseous elemental mercury (Hg
0, Gaseous ElementalMercury, GEM), active gaseous mercury (Hg
2+, Reactive Gaseous Mercury, RGM) and three kinds of particle mercuries (pHg, Particle Mercury is adsorbed in the Atmospheric particulates).Wherein, GEM accounts for about 90% of atmosphere total mercury, and global GEM concentration background value is about 1.5～2.0ng/m
3Because have higher volatility and very low water-soluble, GEM very easily becomes global contaminant by the diffusion mobility of growing distance in general circulation, the mean residence time in atmosphere is about 0.5～2a.
Since the industrial revolution, the mercury release strength of artificial source constantly increases.Research thinks, wherein the burst size of GEM is about 1480t approximately to airborne release 2100t mercury every year for global artificial source.About 500～700 tons/year of China's artificial source atmosphere mercury emission, the more main cause of mercury emissions are China, and the disposal of pollutants Governance Ability is comparatively backward to the demand of the energy is big.Coal-fired and non-ferrous metal metallurgy is the artificial mercury emissions source of two maximums, and average annual discharge capacity accounts for 80% of total release.Under quick urbanization of China and industrialized background, consumption sustainable growths such as fire coal, the atmosphere mercury emission also will constantly rise.
The method of sampling of GEM mainly contains wet absorption method and gold amalgam method in the atmosphere.Wet absorption is with the absorption liquid that contains strong oxidizer, as H
2O
2, KMnO
4-H
2SO
4, K
2Cr
2O
7-HNO
3(all form gaseous mercuries all are oxidized to Hg Deng the gaseous mercury that absorbs in the atmosphere
2+), utilize SnCl then
2Be reduced to Hg
0Steam adopts Cold Atomic Fluorescent Mercury method (CVAFS) or cold-vapour atomic absorption method (CVAAS) to measure at last.Owing to be subjected to the influence of reagent blank, the wet absorption method is subjected to great restriction on using.
Using at present wider is to utilize noble metal (golden mercury-traping tube) such as gold to carry out the sample preenrichment, pyrolysis afterwards, the Hg of release with the principle that mercury forms amalgam at normal temperatures
0Steam enters detecting device analyses such as CVAFS.This method has been eliminated the reagent blank problem in the chemical analysis, have blank low, golden mercury-traping tube and advantage such as can reuse, but still exist analyze consuming time, reappearance is relatively poor, and analysis result is subjected to problems such as the sampling process acidic gas in air influences.Therefore set up that the GEM reliable analytical method is very necessary in the atmosphere.
Summary of the invention
It is strong to the object of the present invention is to provide a kind of simple to operate, favorable reproducibility, anti-error to disturb, and realizes Atmospheric Trace gaseous elemental mercury (GEM) detection by quantitative fast, accurately, and satisfies the analysis requirement of the low detectability of atmosphere GEM.
Technical scheme of the present invention is that the big bicycle pump sample that mercury-traping tube (being generally gold-plated filler) is gathered is carried out pyrolysis release and secondary enrichment, carries out the secondary pyrolysis afterwards and discharges, at last by Cold Atomic Fluorescent Mercury detecting device quantitative test mercury content.
Analytical equipment is made up of parts such as sample pyrolysis release, clarifier, secondary enrichment/pyrolysis release, miniature cooling fan and program controllers.Select for use the nickel chromium triangle material as the sample heater strip, mini-fan is set cools off fast in order to mercury-traping tube, installing CaO powder clarifier is so that remove sour gas.
The structure of apparatus of the present invention is shown in Figure of description.The cavity of sample pyrolysis release (1) is circular quartz glass tube, and the outside twines scratches the nickel chromium triangle heater strip, to realize placing being rapidly heated of mercury-traping tube in the cavity, mini-fan is set simultaneously to realize that mercury-traping tube cools off fast; Clarifier is filled out the CaO powder in (2); The similar of secondary enrichment/pyrolysis release (3) and sample pyrolysis release (1), but mercury-traping tube wherein is the secondary enrichment that is used for mercury; Atomic fluorescence detecting device (4) is used for the quantitative test of mercury vapour; The duty of each parts of program controller (5) tunable control analysis device.
Operating process of the present invention is: the program control analysis operating condition that Atmospheric Trace mercury is set is rapidly heated the Hg of release after the mercury-traping tube of having gathered sample places the pyrolysis release
0Steam enters secondary enrichment/pyrolysis release after removing the acidic components that carries, by mercury-traping tube second adsorption wherein.Afterwards, the mini-fan of pyrolysis release starts, and with quick cooling sample mercury-traping tube, meanwhile, secondary enrichment/pyrolysis release is rapidly heated, the Hg of secondary pyrolysis desorption
0Steam is blown into the Cold Atomic Fluorescent Mercury detecting device by carrier gas and carries out quantitative test.
Characteristics of the present invention are mainly as follows:
(1) the atmosphere GEM sample gathered of mercury-traping tube is released through secondary enrichment and pyrolysis, has reduced the detectability of instrument effectively, satisfies the requirement of atmosphere GEM trace analysis.
(2) Hg that a pyrolysis is discharged
0Steam flow purifies, and reducing sour gas may be to the influence of detecting device generation.
(3) adopt program control technology, analytic process is simple, quick, realizes robotization.
Description of drawings
Figure of description Atmospheric Trace form mercury harvester synoptic diagram
Embodiment
Embodiment 1:
Gather atmosphere GEM sample under the fine weather condition, place described analytical equipment.It is 20～100mL/min that carrier gas (high-purity Ar) flow is set, and sample pyrolysis release is managed interior Hg at 300～700 ℃ of following heated sample mercury-traping tube 10～60s
0Steam is through purifying by the secondary enrichment, at 300～700 ℃ of heating secondary enrichment down/pyrolysis release 0～60s, the Hg that the secondary pyrolysis discharges
0Steam enters the fluorescence detector analysis, and the atmosphere GEM concentration of acquisition is 3.6ng/m
3, the relative deviation of continuous online mercury vapor analyzer monitoring concentration mean value is 3.5% with the same period.
Embodiment 2:
Under the thick weather condition, gather atmosphere GEM sample, place described analytical equipment.It is 20～100mL/min that carrier gas (high-purity Ar) flow is set, and sample pyrolysis release is managed interior Hg at 300～700 ℃ of following heated sample mercury-traping tube 10～60s
0Steam is through purifying by the secondary enrichment, at 300～700 ℃ of heating secondary enrichment down/pyrolysis release 0～60s, the Hg that the secondary pyrolysis discharges
0Steam enters the fluorescence detector analysis, and the atmosphere GEM concentration of acquisition is 5.3ng/m
3, the relative deviation of continuous online mercury vapor analyzer monitoring concentration mean value is 2.9% with the same period.
Claims (5)
1. method and apparatus that is used to analyze trace gaseous elemental mercury (GEM), comprise following apparatus: the cavity of sample pyrolysis release (1) is circular quartz glass tube, the outside twines scratches the nickel chromium triangle heater strip, to realize placing being rapidly heated of sample mercury-traping tube in the cavity, mini-fan is set simultaneously to realize that mercury-traping tube cools off fast; Clarifier is filled out the CaO powder in (2); The similar of secondary enrichment/pyrolysis release (3) and sample pyrolysis release (1), but mercury-traping tube wherein is the secondary enrichment that is used for mercury; Atomic fluorescence detecting device (4) is used for the quantitative test of mercury vapour; The duty of each parts of program controller (5) tunable control analysis device.
2. the analytical approach that is used for atmosphere GEM sample according to claim 1, it is characterized in that: described analytical approach is that the mercury sample is carried out secondary enrichment and secondary pyrolysis release, thereby effectively reduce the detectability of method, satisfy the requirement of atmosphere GEM trace analysis.
3. the analytical approach that is used for atmosphere GEM sample according to claim 1 is characterized in that: described atmosphere GEM sample pyrolysis air-flow purification medium adopts the CaO powder.
4. the analytical approach that is used for atmosphere GEM sample according to claim 1 is characterized in that: described carrier gas (high-purity Ar) flow is 20～100mL/min.
5. the analytical approach that is used for atmosphere GEM sample according to claim 1 is characterized in that: the pyrolysis release temperature of described sample is 300～700 ℃, and be 10～60s heat time heating time, adopts miniature wind type cooling.
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103604892A (en) * | 2013-11-28 | 2014-02-26 | 北京雪迪龙科技股份有限公司 | Mercury monitoring apparatus and mercury monitoring method |
| CN103616269A (en) * | 2013-11-28 | 2014-03-05 | 北京雪迪龙科技股份有限公司 | Mercury monitoring method |
| CN103852370A (en) * | 2014-03-04 | 2014-06-11 | 天津市环境保护科学研究院 | Mobile low-temperature adsorption concentration-thermal desorption device and application method thereof |
| CN105044000A (en) * | 2015-06-29 | 2015-11-11 | 天津师范大学 | Dispersion-free gas phase photometer |
| CN106442606A (en) * | 2016-09-28 | 2017-02-22 | 华中科技大学 | Method and device for recognizing mercury forms |
| CN107389387A (en) * | 2017-06-26 | 2017-11-24 | 杭州超距科技有限公司 | Portable trace mercury analyzer |
| CN107462557A (en) * | 2017-07-31 | 2017-12-12 | 贵州民族大学 | A kind of power plant's Mercury In The Air detection method |
| CN107880970A (en) * | 2017-11-14 | 2018-04-06 | 华北电力大学（保定） | A kind of microwave radiation formula low-temperature pyrolysis of coal demercuration system and application method |
| CN109061063A (en) * | 2018-08-10 | 2018-12-21 | 中国石油天然气股份有限公司 | Tower column structure for evaluating performance of natural gas mercury removing agent |
| CN109142017A (en) * | 2018-09-12 | 2019-01-04 | 河南理工大学 | Separation, collecting device and the method for mercury in a kind of crude oil |
| CN109613181A (en) * | 2018-11-28 | 2019-04-12 | 中国计量科学研究院 | A kind of trace gaseous mercury standard generating system |
| CN109883803A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | A kind of device and method of secondary enrichment parsing |
| CN110462368A (en) * | 2017-03-31 | 2019-11-15 | 拉皮斯坎系统股份有限公司 | The heating of quick desorption device and cooling for trace detection |
| CN110864946A (en) * | 2019-11-13 | 2020-03-06 | 清华大学 | Device and method for measuring mercury content in flue gas |
| CN111398328A (en) * | 2020-04-30 | 2020-07-10 | 江苏天瑞仪器股份有限公司 | On-line monitoring method and monitoring device for concentration of various target elements in flue gas |
| CN112649457A (en) * | 2021-01-15 | 2021-04-13 | 钢研纳克检测技术股份有限公司 | X-ray fluorescence rapid analysis method for trace heavy metal mercury in solid sample |
| CN113884649A (en) * | 2021-11-05 | 2022-01-04 | 中国科学院地球化学研究所 | Automatic analysis device for analyzing gaseous total mercury |
| CN114235761A (en) * | 2021-11-24 | 2022-03-25 | 清华大学 | Fractal-state atmospheric mercury monitoring equipment and monitoring method |
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| CN103604892A (en) * | 2013-11-28 | 2014-02-26 | 北京雪迪龙科技股份有限公司 | Mercury monitoring apparatus and mercury monitoring method |
| CN103616269A (en) * | 2013-11-28 | 2014-03-05 | 北京雪迪龙科技股份有限公司 | Mercury monitoring method |
| CN103604892B (en) * | 2013-11-28 | 2015-09-23 | 北京雪迪龙科技股份有限公司 | A kind of mercury monitoring device and mercury monitoring method |
| CN103852370A (en) * | 2014-03-04 | 2014-06-11 | 天津市环境保护科学研究院 | Mobile low-temperature adsorption concentration-thermal desorption device and application method thereof |
| CN105044000A (en) * | 2015-06-29 | 2015-11-11 | 天津师范大学 | Dispersion-free gas phase photometer |
| CN106442606A (en) * | 2016-09-28 | 2017-02-22 | 华中科技大学 | Method and device for recognizing mercury forms |
| CN106442606B (en) * | 2016-09-28 | 2019-01-15 | 华中科技大学 | A kind of method and apparatus identifying mercury shape |
| CN110462368A (en) * | 2017-03-31 | 2019-11-15 | 拉皮斯坎系统股份有限公司 | The heating of quick desorption device and cooling for trace detection |
| CN107389387A (en) * | 2017-06-26 | 2017-11-24 | 杭州超距科技有限公司 | Portable trace mercury analyzer |
| CN107462557A (en) * | 2017-07-31 | 2017-12-12 | 贵州民族大学 | A kind of power plant's Mercury In The Air detection method |
| CN107880970A (en) * | 2017-11-14 | 2018-04-06 | 华北电力大学（保定） | A kind of microwave radiation formula low-temperature pyrolysis of coal demercuration system and application method |
| CN107880970B (en) * | 2017-11-14 | 2023-10-31 | 华北电力大学（保定） | Microwave radiation type coal low-temperature pyrolysis mercury removal system and use method thereof |
| CN109883803A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | A kind of device and method of secondary enrichment parsing |
| CN109061063A (en) * | 2018-08-10 | 2018-12-21 | 中国石油天然气股份有限公司 | Tower column structure for evaluating performance of natural gas mercury removing agent |
| CN109061063B (en) * | 2018-08-10 | 2021-01-01 | 中国石油天然气股份有限公司 | Tower column structure for evaluating performance of natural gas mercury removing agent |
| CN109142017A (en) * | 2018-09-12 | 2019-01-04 | 河南理工大学 | Separation, collecting device and the method for mercury in a kind of crude oil |
| CN109142017B (en) * | 2018-09-12 | 2023-09-12 | 河南理工大学 | Equipment and method for separating and collecting mercury in crude oil |
| CN109613181A (en) * | 2018-11-28 | 2019-04-12 | 中国计量科学研究院 | A kind of trace gaseous mercury standard generating system |
| CN109613181B (en) * | 2018-11-28 | 2022-03-22 | 中国计量科学研究院 | Trace gaseous mercury standard generation system |
| CN110864946A (en) * | 2019-11-13 | 2020-03-06 | 清华大学 | Device and method for measuring mercury content in flue gas |
| CN111398328A (en) * | 2020-04-30 | 2020-07-10 | 江苏天瑞仪器股份有限公司 | On-line monitoring method and monitoring device for concentration of various target elements in flue gas |
| CN112649457A (en) * | 2021-01-15 | 2021-04-13 | 钢研纳克检测技术股份有限公司 | X-ray fluorescence rapid analysis method for trace heavy metal mercury in solid sample |
| CN113884649A (en) * | 2021-11-05 | 2022-01-04 | 中国科学院地球化学研究所 | Automatic analysis device for analyzing gaseous total mercury |
| CN114235761A (en) * | 2021-11-24 | 2022-03-25 | 清华大学 | Fractal-state atmospheric mercury monitoring equipment and monitoring method |
| CN114235761B (en) * | 2021-11-24 | 2023-01-24 | 清华大学 | Fractal-state atmospheric mercury monitoring equipment and monitoring method |
| WO2023093203A1 (en) * | 2021-11-24 | 2023-06-01 | 清华大学 | Monitoring device and monitoring method for atmospheric mercury in different states |
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Application publication date: 20111019 |