CN101819212A - On-line automatic monitoring device for water quality mercury - Google Patents
On-line automatic monitoring device for water quality mercury Download PDFInfo
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- CN101819212A CN101819212A CN 201010150252 CN201010150252A CN101819212A CN 101819212 A CN101819212 A CN 101819212A CN 201010150252 CN201010150252 CN 201010150252 CN 201010150252 A CN201010150252 A CN 201010150252A CN 101819212 A CN101819212 A CN 101819212A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000012806 monitoring device Methods 0.000 title claims abstract description 22
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- 238000006243 chemical reaction Methods 0.000 claims description 37
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- 239000007788 liquid Substances 0.000 claims description 24
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses an on-line automatic monitoring device for water quality mercury, which is characterized by comprising a PLC control system (5), and a sampling system (1), an oxidation reduction system (2), a gasification system (3) and a measuring system (4) which are connected orderly by a pipeline. The PLC control system is internally equipped with preset programming procedures for controlling operation of the sampling system, the oxidation reduction system, the gasification system and the measuring system; and after sampling by the sampling system, the water sample to be tested forms metallic mercury through treatment by the oxidation reduction system, and then the metallic mercury enters the measuring system for measuring after being gasified by the gasification system. Compared with similar products, the on-line automatic monitoring device has the advantages of lower fault rate, less maintenance, lower reagent consumption, higher price-to-performance ratio and higher accuracy.
Description
Technical field
The invention belongs to the water quality monitoring technical field, be specifically related to a kind of on-line automatic monitoring device for water quality mercury.
Background technology
Having many uses of mercury made the catholyte salt solution with mercury and produced chlorine and caustic soda in chemical industry; Make mercury vapor lamp, vacuum pump, physics instrument (as barometer, thermometer, sphygmomanometer etc.) with mercury; Make various mercurous medicines, reagent, agricultural chemicals, explosive etc.; Extract precious metals such as gold and silver with amalgam process; Handicraft or the temple gold-plated or gold-plating of gold amalgam.In total consumption, mercury metal account for 30%, the mercury of compound state accounts for 70%.Metallurgical industry is used amalgam process (mercury can dissolve other metal and form amalgam) always and is extracted metals such as gold, silver and thallium.Chemical industry is made negative electrode with mercury and is produced caustic soda and chlorine with electrolytic salt solution.Mercury is made pool tube, mercury vacuum pump, novel and alcohol, concentrated nitric acid solution Hybrid Heating are made.Some compounds of mercury are pharmaceutically having sterilization, diuresis and analgesic activity, and the mercury silver alloy is good dental material.On traditional Chinese medicine, mercury is disliked the raw material of sore, mange medicine as treatment.Mercury can be used as mold and the cooling medium of atomic pile and the constituent element of cadmium base bearing alloy etc. of hot investment casting.
But mercury and compound thereof belong to extremely toxic substance, can accumulate in human body.The main source of these mercury is instrucment and meter plant, salt electrolysis, precious metal smelting, cosmetics, illuminator lamp, dental material, fire coal, hydrobiont etc.After mercury metal in the blood enters brain tissue, accumulate in brain tissue gradually, will cause damage to brain tissue when reaching certain amount, a part of in addition mercury ion is transferred to kidney.The inorganic mercury ion that enters water body can change the bigger organic mercury of toxicity into, enters human body by food chain, causes the whole body intoxication; Vulnerable crowd has the women, especially ready-to-be mother, hobby seafood personage; Mercurous few in the natural water, generally be no more than 0.1 μ g/L.Mercury is one of index of China's enforcement total emission volumn control.
The environmental protection industry standard HJ/T 241-2007 of the People's Republic of China (PRC) discloses " the mensuration Cold Atomic Fluorescent Mercury method (trying) of water quality mercury " tentative standard, and its principle is: the mercury ion in the water sample is reduced agent and is reduced to simple substance mercury, forms mercury vapour.Its ground state mercury atom is subjected to the ultraviolet excitation of wavelength 253.7nm, just gives off the fluorescence of identical wavelength when excited state mercury atom deexcitation.Under given condition and in the lower concentration range, fluorescence intensity is directly proportional with the concentration of mercury.Under laboratory condition, the mensuration of water quality mercury realizes by the digital phosphor mercury vapor analyzer, yet still do not carry out the equipment of water quality online auto monitoring water quality mercury in the prior art.The present invention comes therefrom.
Summary of the invention
The object of the invention is to provide a kind of on-line automatic monitoring device for water quality mercury, has solved that the equipment that lacks online auto monitoring water quality mercury in the prior art causes that monitoring water quality on line work is loaded down with trivial details, program repeat, measurement result have problems such as human factor is accurate inadequately.
In order to solve these problems of the prior art, technical scheme provided by the invention is:
A kind of on-line automatic monitoring device for water quality mercury is characterized in that described device comprises sampling system, oxidation-reduction system, gasification system and mensuration system that the PLC control system is connected with pipeline successively; Default program in the described PLC control system, control sampling system, oxidation-reduction system, gasification system and mensuration system works, described sampling system sampling back water sample to be measured is handled through oxidation-reduction system and is formed mercury metal, and described mercury metal enters the mensuration system measurement after the gasification system gasification.
Preferably, described mensuration system comprises measuring cell, and described measuring cell one end is provided with drying device, the other end is provided with the mercury vapour absorption plant, described gasification system after enter measuring cell after the drying device drying and measure, enters mercury metal gasification then the mercury vapour absorption plant and absorbs, and residual air is discharged.
Preferably, described oxidation-reduction system comprises reaction bulb, described reaction bulb arranged outside attemperator, and described reaction bulb lower end is connected with gasification system by pipeline.
Preferably, described device also comprises waste liquid bottle, and described waste liquid bottle is communicated with reaction bulb control by pipeline, and after the mensuration system measurement finished, waste liquid was collected into the waste liquid bottle discharge by the road in the reaction bulb.
Preferably, open and close pipeline connection by the multi-way selecting valve selectivity between described reaction bulb and waste liquid bottle, after the mensuration system measurement finished, multi-way selecting valve was opened the pipeline connection effluent discharge of reaction bulb and waste liquid bottle.
Preferably, be communicated with by the multi-way selecting valve pilot piping between described reaction bulb and gasification system.
Preferably, described gasification system comprises air pump, and described air pump is communicated with the oxidation-reduction system pilot piping by multi-way selecting valve.
Preferably, described sampling system comprises the peristaltic pump that is used for sample introduction in oxidation-reduction system, is provided for accurately measuring the photoelectrometer buret of water sample or reagent on the pipeline of described peristaltic pump; Described peristaltic pump passes through pump water sampling or reagent, and water sample or reagent are sent in the oxidation-reduction system.
Preferably, be communicated with by the multi-way selecting valve pilot piping between described peristaltic pump and water sample to be measured or reagent; Described multi-way selecting valve selectivity opens and closes water sample pipeline to be measured, standard model pipeline, distilled water pipeline, oxygenant reagent pipeline, rare HNO
3Solution reagent pipeline, the first reductive agent reagent pipeline and the second reductive agent reagent pipeline.
Preferably, be communicated with air pump by three-way solenoid valve control on the connecting line of described peristaltic pump and multi-way selecting valve; When sampling system was worked, three-way solenoid valve was opened the pipeline connection of sampling system and oxidation-reduction system; When gasification system was worked, three-way solenoid valve was opened the pipeline connection of gasification system and oxidation-reduction system.
Preferably, described peristaltic pump comprises stepper motor driven roller, and described roller is arranged on the outside of pipeline, and described stepper motor is got reagent or sample according to the instruction driving rolls rotation negative pressure pump of PLC control system.Described photoelectrometer buret comprises the gauge line of determining volume, the two ends scale arranged outside photoelectric detector of described gauge line; Described photoelectric detector is according to having or not of reagent in the gauge line or sample accurate meters reagents or the volume of sample.
The present invention adopts the principle in " the mensuration cold atom absorptiometry of GB7468-87 water quality total mercury ": under the condition of sulfonitric medium and heating, with potassium permanganate and potassium persulfate under little condition of boiling, with sample digestion, make the mercurous dimercurion that all is converted in the sample.With the oxygenant reduction of oxammonium hydrochloride, with stannous chloride divalence mercury is reduced into mercury metal again with surplus.At room temperature bubbling air is written into absorption tube with the mercury metal steam, measures its absorption value at 253.7nm wavelength place, and within the specific limits, absorption value is directly proportional with the mercury vapour amount, can try to achieve the content of mercury in the sample in view of the above.
After the measurement cyclic process begins, wash each pipeline, gauge line and reaction bulb with new water sample earlier, to remove residual chaff interference.The sampling of PLC control system control sampling system uses peristaltic pump with water sample, oxygenant, rare HNO
3Solution, first reductive agent, second reductive agent successively are added to reaction under insulation (temperature constant) and acid condition in the reaction bulb by the order of programming in advance; Pass through the gasification system bubbling air after reacting completely with mercury vapourization, be written into measuring cell after the mercury vapour drying device internal desiccant drying; Utilize cold-vapour atomic absorption method to measure absorbance then, calculate the concentration of mercury in the water sample according to absorbance.The mercury vapour absorption cell of measuring cell one end setting absorbs the mercury vapour by measuring cell, the control mercury pollution.
In whole measurement cyclic process, owing to adopt peristaltic pump to carry out the sample introduction sampling, water sample and reagent solution just enter reaction bulb by pipeline, and liquid does not directly contact with peristaltic pump, prevent from the corrosion and the chaff interference of peristaltic pump are polluted; And the photoelectrometer buret is set on the pipeline of peristaltic pump, can prevent to produce the error of the liquid volume added that causes owing to the peristaltic pump fluctuations in discharge.Certainly,, in reaction bulb, pass through the bubbling mixing material, thereby guarantee that the solution in the reaction bulb mixes fully in order to react quickening or to react more complete.
With respect to scheme of the prior art, advantage of the present invention is:
1. on-line automatic monitoring device for water quality mercury of the present invention adopts the measuring method of cold-vapour atomic absorption method as online automatic monitor.Its sampling system adopts peristaltic pump sampling, and the reagent sample introduction adopts peristaltic pump negative pressure suction, guarantee the contact of liquid discord pump line, stopped pump line to the pollution of liquid, avoided the pump line corrosion.The photoelectrometer buret is set on the sampling line, utilizes the photoelectric metering guard system to overcome the error that the peristaltic pump instability of flow causes; Realize the accurate quantification of trace reagent simultaneously, significantly reduced the reagent use amount.
2, adopt the whole device of PLC control system control in the technical solution of the present invention, the PLC control system is programmed in advance, measuring cyclic process can carry out repeatedly, makes this product have less trouble more, lower maintenance, lower reagent consumption and higher cost performance and accuracy than like product.Oxidation-reduction system adopts temperature controlled reaction bulb, reduces the influence of temperature to measurement result, adopts the temperature conditions of strict control, guarantees that reaction conditions meets the requirements, even is better than manually-operated.
3, adopt multi-way selecting valve in the preferred technical solution of the present invention, versatile and flexible with communication passage such as each reagent bottle, sample, waste liquids, abandoned expensive diaphragm electromagnetic valve, greatly reduce maintenance and maintenance cost, also make apparatus structure compactness of the present invention, be convenient to preparation and production.Multi-way selecting valve is communicated with by PLC control system pilot piping, few consumable accessory, and failure rate is low, and operating cost is low.In addition, by the PLC control system can fault, when exceeding standard active retrograde to warning.
Description of drawings
Below in conjunction with drawings and Examples the present invention is further described:
Fig. 1 is the schematic diagram of embodiment of the invention on-line automatic monitoring device for water quality mercury;
Fig. 2 is the pipeline connecting figure of embodiment of the invention on-line automatic monitoring device for water quality mercury.
Wherein: 1 is sampling system; 2 is oxidation-reduction system; 3 is gasification system; 4 is the mensuration system; 5 is the PLC control system; 6 is waste liquid bottle; 7 is three-way solenoid valve;
11 is peristaltic pump; 12 is the photoelectrometer buret; 13 is multi-way selecting valve; 21 is reaction bulb; 22 is attemperator; 31 is air pump; 41 is measuring cell; 42 is drying device; 43 is the mercury vapour absorption plant; 100 is water sample pipeline to be measured; 101 is that standard model pipeline, 102 is that distilled water pipeline, 103 is that oxygenant reagent pipeline, 104 is rare HNO
3Solution reagent pipeline, 105 is that the first reductive agent reagent pipeline, 106 is the second reductive agent reagent pipeline.
Embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are used to the present invention is described and are not limited to limit the scope of the invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
The embodiment on-line automatic monitoring device for water quality mercury
As depicted in figs. 1 and 2, this on-line automatic monitoring device for water quality mercury comprises sampling system 1, oxidation-reduction system 2, gasification system 3 and mensuration system 4 that PLC control system 5 is connected with pipeline successively; Default program in the described PLC control system, control sampling system, oxidation-reduction system, gasification system and mensuration system works, described sampling system sampling back water sample to be measured is handled through oxidation-reduction system and is formed mercury metal, and described mercury metal enters the mensuration system measurement after the gasification system gasification.
Sampling system comprises the peristaltic pump 11 that is used for sample introduction in oxidation-reduction system, is provided for accurately measuring the photoelectrometer buret 12 of water sample or reagent on the pipeline of described peristaltic pump; Described peristaltic pump passes through pump water sampling or reagent, and water sample or reagent are sent in the oxidation-reduction system.Be communicated with by multi-way selecting valve 13 pilot piping between described peristaltic pump and water sample to be measured or reagent; Described multi-way selecting valve 13 selectivity open and close water sample pipeline 100 to be measured, standard model pipeline 101, distilled water pipeline 102, oxygenant reagent pipeline 103, rare HNO
3Solution reagent pipeline 104, the first reductive agent reagent pipeline 105, the second reductive agent reagent pipeline 106 and waste liquid bottle 6 pipelines.Peristaltic pump comprises stepper motor driven roller, and described roller is arranged on the outside of pipeline, and described stepper motor is got reagent or sample according to the instruction driving rolls rotation negative pressure pump of PLC control system.Described photoelectrometer buret comprises the gauge line of determining volume, the two ends scale arranged outside photoelectric detector of described gauge line; Described photoelectric detector is according to having or not of reagent in the gauge line or sample accurate meters reagents or the volume of sample.
Oxidation-reduction system comprises reaction bulb 21, described reaction bulb 21 arranged outside attemperators 22, and described reaction bulb lower end is connected with gasification system 3 by pipeline.Described waste liquid bottle 6 is communicated with reaction bulb 21 controls by pipeline, and after the mensuration system measurement finished, waste liquid was collected into the waste liquid bottle discharge by the road in the reaction bulb.6 of described reaction bulb 21 and waste liquid bottles pass through multi-way selecting valve 13 selectivity and open and close pipeline connection, and after the mensuration system measurement finished, multi-way selecting valve was opened the pipeline connection effluent discharge of reaction bulb and waste liquid bottle.
Gasification system 3 comprises air pump 31, and described air pump is communicated with the oxidation-reduction system pilot piping by multi-way selecting valve 13.3 of described reaction bulb and gasification systems are communicated with by multi-way selecting valve 13 pilot piping.Be communicated with air pump 31 by three-way solenoid valve 7 controls on the connecting line of described peristaltic pump 11 and multi-way selecting valve 13; When sampling system was worked, three-way solenoid valve 7 was opened the pipeline connection of sampling system and oxidation-reduction system; When gasification system 3 work, three-way solenoid valve 7 is opened the pipeline connection of gasification system and oxidation-reduction system.
Pipeline adopts the fluorine tubes of material of 1.5mm internal diameter in the device.After the measurement cyclic process begins, wash each pipeline, gauge line and reaction bulb with new water sample earlier, to remove residual chaff interference.The sampling of PLC control system control sampling system uses peristaltic pump with water sample, oxygenant, rare HNO
3Solution, first reductive agent, second reductive agent successively are added to reaction under insulation (temperature constant) and acid condition in the reaction bulb by the order of programming in advance; Pass through the gasification system bubbling air after reacting completely with mercury vapourization, be written into measuring cell after the mercury vapour drying device internal desiccant drying; Utilize cold-vapour atomic absorption method to measure absorbance then, calculate the concentration of mercury in the water sample according to absorbance.The mercury vapour absorption cell of measuring cell one end setting absorbs the mercury vapour by measuring cell, prevents and remedies pollution.
Above-mentioned example only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (10)
1. on-line automatic monitoring device for water quality mercury is characterized in that described device comprises sampling system (1), oxidation-reduction system (2), gasification system (3) and mensuration system (4) that PLC control system (5) is connected with pipeline successively; Default program in the described PLC control system, control sampling system, oxidation-reduction system, gasification system and mensuration system works, described sampling system sampling back water sample to be measured is handled through oxidation-reduction system and is formed mercury metal, and described mercury metal enters the mensuration system measurement after the gasification system gasification.
2. on-line automatic monitoring device for water quality mercury according to claim 1, it is characterized in that described mensuration system (4) comprises measuring cell (41), described measuring cell one end is provided with drying device (42), the other end is provided with mercury vapour absorption plant (43), described gasification system gasifies mercury metal after enter the measuring cell measurement after the drying device drying, enter the mercury vapour absorption plant then and absorb, residual air is discharged.
3. on-line automatic monitoring device for water quality mercury according to claim 1, it is characterized in that described oxidation-reduction system comprises reaction bulb (21), described reaction bulb (21) arranged outside attemperator (22), described reaction bulb lower end is connected with gasification system (3) by pipeline.
4. on-line automatic monitoring device for water quality mercury according to claim 3, it is characterized in that described device also comprises waste liquid bottle (6), described waste liquid bottle is communicated with reaction bulb (21) control by pipeline, and after the mensuration system measurement finished, waste liquid was collected into the waste liquid bottle discharge by the road in the reaction bulb.
5. on-line automatic monitoring device for water quality mercury according to claim 4, it is characterized in that opening and closing pipeline connection by multi-way selecting valve (13) selectivity between described reaction bulb (21) and waste liquid bottle (6), after the mensuration system measurement finished, multi-way selecting valve was opened the pipeline connection effluent discharge of reaction bulb and waste liquid bottle.
6. on-line automatic monitoring device for water quality mercury according to claim 3 is characterized in that being communicated with by multi-way selecting valve (13) pilot piping between described reaction bulb and gasification system (3).
7. on-line automatic monitoring device for water quality mercury according to claim 1 is characterized in that described gasification system (3) comprises air pump (31), and described air pump is communicated with the oxidation-reduction system pilot piping by multi-way selecting valve (13).
8. on-line automatic monitoring device for water quality mercury according to claim 7, it is characterized in that described sampling system comprises the peristaltic pump (11) that is used for sample introduction in oxidation-reduction system, is provided for accurately measuring the photoelectrometer buret (12) of water sample or reagent on the pipeline of described peristaltic pump; Described peristaltic pump passes through pump water sampling or reagent, and water sample or reagent are sent in the oxidation-reduction system.
9. on-line automatic monitoring device for water quality mercury according to claim 8 is characterized in that being communicated with by multi-way selecting valve (13) pilot piping between described peristaltic pump and water sample to be measured or reagent; Described multi-way selecting valve (13) selectivity opens and closes water sample pipeline to be measured (100), standard model pipeline (101), distilled water pipeline (102), oxygenant reagent pipeline (103), rare HNO
3Solution pipeline (104), the first reductive agent reagent pipeline (105) and the second reductive agent reagent pipeline (106).
10. on-line automatic monitoring device for water quality mercury according to claim 8 is characterized in that being communicated with air pump (31) by three-way solenoid valve (7) control on the connecting line of described peristaltic pump (11) and multi-way selecting valve (13); When sampling system was worked, three-way solenoid valve (7) was opened the pipeline connection of sampling system and oxidation-reduction system; When gasification system (3) was worked, three-way solenoid valve (7) was opened the pipeline connection of gasification system and oxidation-reduction system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010150252 CN101819212B (en) | 2010-04-15 | 2010-04-15 | On-line automatic monitoring device for water quality mercury |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 201010150252 CN101819212B (en) | 2010-04-15 | 2010-04-15 | On-line automatic monitoring device for water quality mercury |
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| CN102252881A (en) * | 2011-04-27 | 2011-11-23 | 杭州慕迪科技有限公司 | On-line monitoring device of cyanides in water |
| CN102262087A (en) * | 2011-04-27 | 2011-11-30 | 杭州慕迪科技有限公司 | On-line monitoring device for total arsenic in water quality |
| CN103499558A (en) * | 2013-09-06 | 2014-01-08 | 深圳市中兴环境仪器有限公司 | System and method for determining mercury concentration in water |
| CN104007076A (en) * | 2014-06-06 | 2014-08-27 | 郝俊 | Method for detecting mercury in sewage |
| CN104897587A (en) * | 2015-05-20 | 2015-09-09 | 上海淼通检测技术发展有限公司 | On-line water quality analysis method |
| CN105467140A (en) * | 2014-09-29 | 2016-04-06 | 东亚Dkk株式会社 | Mercury automatic detection system and pre-processing device thereof |
| CN106680520A (en) * | 2017-02-04 | 2017-05-17 | 宁波亿诺维信息技术有限公司 | Water quality automatic detection analyzer |
| CN106885914A (en) * | 2017-03-05 | 2017-06-23 | 宁波亿诺维信息技术有限公司 | Multi-pollutant is into different water automatic detection analysis instrument and detection method |
| CN107817236A (en) * | 2017-12-14 | 2018-03-20 | 浙江微兰环境科技有限公司 | A kind of water quality total mercury detection means of ultraviolet digestion Pressurized sample digestion |
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| CN104007076A (en) * | 2014-06-06 | 2014-08-27 | 郝俊 | Method for detecting mercury in sewage |
| CN105467140A (en) * | 2014-09-29 | 2016-04-06 | 东亚Dkk株式会社 | Mercury automatic detection system and pre-processing device thereof |
| CN105467140B (en) * | 2014-09-29 | 2018-07-31 | 东亚Dkk株式会社 | Mercury automatic checkout system and its pretreatment unit |
| CN104897587A (en) * | 2015-05-20 | 2015-09-09 | 上海淼通检测技术发展有限公司 | On-line water quality analysis method |
| CN106680520A (en) * | 2017-02-04 | 2017-05-17 | 宁波亿诺维信息技术有限公司 | Water quality automatic detection analyzer |
| CN106885914A (en) * | 2017-03-05 | 2017-06-23 | 宁波亿诺维信息技术有限公司 | Multi-pollutant is into different water automatic detection analysis instrument and detection method |
| CN107817236A (en) * | 2017-12-14 | 2018-03-20 | 浙江微兰环境科技有限公司 | A kind of water quality total mercury detection means of ultraviolet digestion Pressurized sample digestion |
| CN107817236B (en) * | 2017-12-14 | 2024-04-16 | 浙江微兰环境科技有限公司 | Water quality total mercury detection device adopting ultraviolet digestion cold atomic fluorescence method |
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