CN109900769A - The method and device of ammonia nitrogen in a kind of ion mobility spectrometry quantitative measurment water - Google Patents
The method and device of ammonia nitrogen in a kind of ion mobility spectrometry quantitative measurment water Download PDFInfo
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- CN109900769A CN109900769A CN201711290348.9A CN201711290348A CN109900769A CN 109900769 A CN109900769 A CN 109900769A CN 201711290348 A CN201711290348 A CN 201711290348A CN 109900769 A CN109900769 A CN 109900769A
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- ion mobility
- mobility spectrometry
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- ammonia nitrogen
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Abstract
The invention discloses the new methods and device of ammonia nitrogen in a kind of ion mobility spectrometry quantitative measurment water.The basic principle of this method is to react to generate ammonia with alkali using ionic migration spectrometer quantitative measurment sample, so that the ammonia nitrogen in water be enable to measure.Apparatus of the present invention include: the composition such as constant-temperature heating sleeve, ion mobility spectrometry, flowmeter, reactor, reaction substrate, threeway, mass flowmenter, micro syringe, four fluorine tube.This method has sampling amount few, detection time is short (< 30s), detection limits the advantages that low (< 0.01mg/L), can meet the fast high-flux measurement of ammonia-nitrogen content in the various water samples such as surface water, underground water, municipal wastewater.
Description
Technical field
The present invention relates to a kind of method and device of ammonia nitrogen in ion mobility spectrometry quantitative measurment water, specially a kind of detection limit
Up to the new method for carrying out highly sensitive, high-throughput rapid survey to ammonia nitrogen in water of 0.1mg/L.This patent discusses the device
The contents such as composition, construction, testing principle, measurement method.The present invention has detection time short (< 30s), and detection limits low (<
0.01mg/L) the features such as, can meet the fast high-flux of ammonia-nitrogen content in the various water samples such as surface water, underground water, municipal wastewater
Measurement.
Background technique
With the rapid development of our country's economy with the lag of environment measuring means and safeguard measure, a large amount of industry and life are useless
Water is directly discharged into river, lake, until ocean.Wherein contain a large amount of ammonia nitrogen compound, destroys water environment, cause water body
Eutrophication has directly threatened the safety of resident living drinking water.Therefore, ammonia nitrogen is referring mainly to for China's water body environment monitoring
One of mark.
Currently, spectrophotometry, gas molecule in space absorption process, electrode method etc. are the normal of ammonia-nitrogen content in experimental determination water body
Use method.The preci-sion and accuracy of spectrophotometry is higher, be suitable for trace measurement, but to experiment condition, reagent purity and
Personnel qualifications are higher, it is difficult to be applied to outdoor live quick online detection, be of limited application.Gas-phase molecular absorption spectrometry
Method has many advantages, such as that strong interference immunity, measurement are accurate, and measurement range is larger, but its instrument cost is higher, to peopleware
It is required that it is also higher, it is of limited application.Electrode method have does not need to pre-process water sample, influenced by the turbidity of water sample it is small,
The advantages that operating cost is lower, but its electrode is easy by surface active agent pollution in water, and service life is limited.Occur in recent years
The new method of some measurement ammonia nitrogens, such as Flow Injection Analysis, Blow-off-conductometry, enzyme process, but equipment needed for this method is more multiple
Miscellaneous, higher cost is also verified without market practice, and distance field is quickly detected will walk there are also very long stretch.
Ion mobility spectrometry (IMS) is higher with sensitivity, detection is quick, structure is simple and convenient to operate, is cheap, body
The advantages that product is smaller, power consumption is lower, and do not need special chemical reagent.Therefore it is suitble to the needs of field quick detection, quilt
It is widely used in the fields such as drugs inspection, chemical warfare agent and explosive safety check, biological medicine and environment measuring.
Early period, we have developed the technologies of ion mobility spectrometry fast slowdown monitoring Ammonia in Atmosphere online, and had declared specially
Benefit.In conjunction with the working foundation and experimental data of early period, we have gradually carried out the research application of Ammonia Nitrogen in Aquatic Environment.As a result, originally
Patent is based on Ion mobility spectrometry, devises the new method and device of ammonia nitrogen in a kind of ion mobility spectrometry quantitative measurment water, real
Now the fast high-flux of ammonia-nitrogen content in water is measured.
Summary of the invention
The new method and device of ammonia nitrogen in a kind of ion mobility spectrometry quantitative measurment water
The technical solution adopted by the invention is as follows:
Detection device includes: microsyringe or micro syringe, reactor, solid alkaline reaction substrate, threeway, ion
Migration spectrum, thermostat；
Reactor is a closed container, and solid alkaline reaction substrate is placed in reactor, and reactor top Lettuce has load
Gas entrance pipe, carrier gas inlet pipeline one end are connected with carrier gas source, and the other end stretches to the middle and lower part in reactor, micro-sampling
The injection port or micro syringe syringe needle of device stretch to inside reactor from reactor top, and reactor head is equipped with and threeway
The connected gas vent of first interface, second interface of threeway are connected with the injection port of ion mobility spectrometry, the third of threeway
A interface emptying；
Thermostat includes the hollow housing of upper end opening, and housing outer surface is enclosed with insulating layer, is equipped with heating in shell
Stick and temperature sensor, temperature sensor are connect with temperature controller signal, and heating rod passes through temperature controller and external power phase
Even.
Ion mobility spectrometry gas circuit includes drift port, injection port, tail gas mouth；Gas is floated through the first mass flowmenter and Ion transfer
Spectrum drift port is connected；The tail gas of ion mobility spectrometry tail gas mouth is connected through mass flowmenter with the air inlet of vacuum pump；Tail gas is through
Two mass flowmenters are discharged by vacuum pump；The output signal of ion mobility spectrometry is through signal amplifier and signal acquisition and display equipment
It is connected；React the NH generated3, under the action of carrier gas, ion mobility spectrometry is reached through threeway, is detected.Ion mobility spectrometry hair
Electric signal out is through signal amplifier by signal acquisition and display equipment output (such as computer).
The material of reactor is polytetrafluoroethylene (PTFE), and upper open end is sealed by silica gel bottle stopper, and the lower end of reactor is in back taper
Shape；There are input, output two-way polytetrafluoroethylene (PTFE) gas conduit beyond the Great Wall in silica gel bottle, the input gas conduit in reactor is longer,
Output duct is shorter；Sample pierces through silica gel bottle stopper by microsyringe or micro syringe and is added in reactor.
Solid alkaline reaction substrate in reactor is dry strongly alkaline compound, can be caustic soda, quick lime, oxidation
One or more of potassium etc., form are particulate solid；One-time pad amount can be certain certain value of 1g into 30g, carrier gas
To purify air.
Pass through the ammonia nitrogen in ion mobility spectrometry quantitative measurment water；In the positive-ion mode, the water sample of the ammonia nitrogen containing known concentration,
It is added in reactor, is reacted with solid alkaline reaction substrate therein, product is with load through microsyringe or micro syringe
Gas reaches ion mobility spectrometry through threeway and is detected, and obtains the ion transfer spectrogram of standard specimen；
Unknown concentration sample water is added in reactor through microsyringe or micro syringe, with solid base therein
Property reaction substrate reaction, product with carrier gas through threeway reach ion mobility spectrometry detected, obtain the ammonia nitrogen ion of unknown sample
Migrate spectrogram；The ion transfer spectrogram of the ion transfer spectrogram of standard sample and unknown sample is compared, is obtained in unknown sample
The concentration of ammonia nitrogen.
It is added in reactor by the ammonia nitrogen in sample by micro syringe, reacts generation with solid alkaline reaction substrate
Product NH3；
The excessive gas of carrier gas and reactor generation is discharged using threeway；Pass through the first quality flowmeter flow quantity and second
Throughput in the flow control ion mobility spectrometry of mass flowmenter；Pass through the flow of quality flowmeter flow quantity and mass flowmenter
Difference, make ion mobility spectrometry extracted from threeway needed for detect sample size.
Electricity in thermostat adds stick, connect through temperature controller with external circuit；Thermostat temperature can maintain 30 DEG C
To a certain particular value in 180 DEG C, usual 50 DEG C to 180 DEG C of a certain particular value.
Advantages of the present invention is as follows:
1. the method for the present invention can ammonia-nitrogen content in the directly detection water body example of scene, single sample analysis time is short
(< 30s) meets the needs that the big flux in scene quickly detects.
2. the ammonia nitrogen in the method for the present invention and device measurement water body, apparatus structure is simple, cost and operating cost are lower.
3. amount of reagent needed for the method for the present invention and device is few, easy to operate, lower to the requirement of operator's specialized capability, just
In popularization and application.
Detailed description of the invention
Fig. 1 is the device figure of ammonia nitrogen in ion mobility spectrometry quantitative measurment water, wherein 1 is micro syringe, and 2 be reactor,
3 substrates, 4 be threeway, and 5 be ion mobility spectrometry, and 6 be the first mass flowmenter, and 7 be the second mass flowmenter, and 8 be vacuum pump, and 9 are
Amplifier 10 is signal acquisition and display equipment, 11 be thermostat, 12 be heating rod, 13 be temperature sensing, 14 be heat preservation
Layer, 15 are temperature control system.
Fig. 2 is the ion transfer spectrogram of blank sample.
Fig. 3 is the ion transfer spectrogram of ammonia nitrogen in water body.
Fig. 4 is the ion transfer spectrogram that same amount ammonia nitrogen is measured after increasing sampling quantity.
Specific embodiment
The use that the following examples illustrate the invention, but the application range is not limited.
The device include: microsyringe or micro syringe 1, reactor 2, solid alkaline reaction substrate 3, threeway 4, from
Sub- migration spectrum 5, thermostat 11；
Device result: reactor 2 is a closed container, and solid alkaline reaction substrate 3 is placed in reactor 2, on reactor 2
Portion's Lettuce has carrier gas inlet pipeline, and carrier gas inlet pipeline one end is connected with carrier gas source, and the other end stretches in reactor 2
Lower part, the injection port or micro syringe syringe needle of microsyringe stretch to inside reactor 2 from 2 top of reactor, reactor 2
Top is equipped with the gas vent that is connected with first interface of threeway 4, second interface of threeway 4 and ion mobility spectrometry 5 into
Sample mouth is connected, the third interface emptying of threeway 4；Warm device 11 includes the hollow housing of upper end opening, housing outer surface package
There is insulating layer 15, heating rod 12 and temperature sensor 13 are equipped in shell, temperature sensor 13 and 15 signal of temperature controller connect
It connects, heating rod 12 is connected by temperature controller 15 with external power.5 gas circuit of ion mobility spectrometry includes drift port, injection port, tail gas
Mouthful；Drift gas is connected through the first mass flowmenter 6 with ion mobility spectrometry drift port；The tail gas of 5 tail gas mouth of ion mobility spectrometry is through quality
Flowmeter 7 is connected with the air inlet of vacuum pump 8；Tail gas is discharged through the second mass flowmenter 7 by vacuum pump 8；Ion mobility spectrometry 5
Output signal is connected through signal amplifier 9 with signal acquisition and display equipment 10；React the NH generated3, under the action of carrier gas,
Ion mobility spectrometry 5 is reached through threeway 4, is detected.Ion mobility spectrometry 5) issue electric signal adopted through signal amplifier 9 by signal
Collection and display equipment 10 export (such as computer).
Embodiment 1
When the new method of ammonia nitrogen and device work in a kind of ion mobility spectrometry quantitative measurment water, migration area voltage is set as
400V/cm, drift throughput are set as 400ml/min, and carrier gas flux is set as 200ml/min, and exhaust flow is set as 500ml/min, adopts
Sample amount is 200ml/min, and extra 200ml/min gas is discharged by threeway in carrier gas.When measuring blank sample, ion is moved
There is a small peak at a reagent reactant ion peak and left side 4.62ms at 4.98ms during shifting spectrogram is main, as shown in Figure 2.
Embodiment 2
It is identical in instrument parameter such as case study on implementation 1.As shown in figure 3, when containing ammonia nitrogen in sample, the spectrum of ion mobility spectrometry
In addition to occurring a new peak at 4.26ms other than 4.98ms goes out and has a peak in figure, the small peak at 4.62ms disappears.4.98ms place
It decreases when peak intensity is compared with no ammonia nitrogen.The content of ammonia nitrogen in water body can be measured according to the intensity at peak at 4.26ms.Pass through measurement
The concentration of series standard sample obtains a series of peak intensity at 4.26ms, and makes calibration curve.Measurement unknown sample obtains it
The intensity at peak at 4.26ms, and compared with calibration curve, obtain the content of ammonia nitrogen in unknown sample.The detection time of this method
< 30s, detection limit < 0.01mg/L, can meet the quick of ammonia-nitrogen content in the various water samples such as surface water, underground water, municipal wastewater
High pass measurement.
Embodiment 3
Sampling quantity can be increased by increasing 7 flow of the second mass flowmenter.As shown in figure 4, constant in other conditions
In the case of, by 7 flow of the second mass flowmenter, i.e. exhaust flow is set as 700ml/min, in ion mobility spectrometry, spectrogram it is unknown
It is unchanged, and the signal of ammonia nitrogen is remarkably reinforced.Therefore, sampling quantity can be increased, to obtain by the method for increase exhaust flow
Obtain lower detection limit.The flow that tail gas can also be reduced as needed, measures the sample of higher concentration.
Claims (9)
1. the device of ammonia nitrogen in a kind of ion mobility spectrometry quantitative measurment water, it is characterised in that:
Device includes:
Detection device includes: microsyringe or micro syringe (1), reactor (2), solid alkaline reaction substrate (3), threeway
(4), ion mobility spectrometry (5), thermostat (11)；
Reactor (2) is a closed container, and solid alkaline reaction substrate (3) is placed in reactor (2), reactor (2) top oil
Mai Caiyou carrier gas inlet pipeline, carrier gas inlet pipeline one end are connected with carrier gas source, under the other end stretches in reactor (2)
Portion, the injection port or micro syringe syringe needle of microsyringe stretch to reactor (2) inside, reaction from reactor (2) top
The gas vent being connected with first interface of threeway (4) is equipped at the top of device (2), second interface of threeway (4) is moved with ion
The injection port for moving spectrum (5) is connected, the third interface emptying of threeway (4)；
Thermostat (11) includes the hollow housing of upper end opening, and housing outer surface is enclosed with insulating layer (15), is equipped in shell
Heating rod (12) and temperature sensor (13), temperature sensor (13) are connect with temperature controller (15) signal, heating rod (12)
It is connected by temperature controller (15) with external power.
2. the device of ammonia nitrogen in a kind of ion mobility spectrometry quantitative measurment water according to claim 1, it is characterised in that: ion
Migration spectrum (5) gas circuit includes drift port, injection port, tail gas mouth；It floats gas and floats gas through the first mass flowmenter (6) and ion mobility spectrometry
Mouth is connected；The tail gas of ion mobility spectrometry (5) tail gas mouth is connected through mass flowmenter (7) with the air inlet of vacuum pump (8)；Tail gas warp
Second mass flowmenter (7) is discharged by vacuum pump (8)；The output signal of ion mobility spectrometry (5) is through signal amplifier (9) and signal
Acquisition and display equipment (10) are connected；React the NH generated3, under the action of carrier gas, ion mobility spectrometry is reached through threeway (4)
(5), it is detected；The electric signal that ion mobility spectrometry (5) issues is through signal amplifier (9) by signal acquisition and display equipment (10)
It exports (such as computer).
3. the device of ammonia nitrogen in a kind of ion mobility spectrometry quantitative measurment water according to claim 2, it is characterised in that: reaction
The material of device (2) is polytetrafluoroethylene (PTFE), and upper open end is sealed by silica gel bottle stopper, and the lower end of reactor (2) is in back taper；In silicon
Glue bottle has input, output two-way polytetrafluoroethylene (PTFE) gas conduit beyond the Great Wall, and the input gas conduit in reactor (2) is longer, output
Conduit is shorter；Sample pierces through silica gel bottle stopper by microsyringe or micro syringe (1) and is added in reactor (2).
4. the device of ammonia nitrogen in a kind of ion mobility spectrometry quantitative measurment water according to claim 2, it is characterised in that: reaction
Solid alkaline reaction substrate (3) in device (2) is dry strongly alkaline compound, can be in caustic soda, quick lime, potassium oxide etc.
One or more, form be particulate solid；One-time pad amount can be certain certain value of 1g into 30g, and carrier gas is drying
Air.
5. a kind of method of ammonia nitrogen in ion mobility spectrometry quantitative measurment water, using any described device of claim 1-4, feature
It is:
Pass through the ammonia nitrogen in ion mobility spectrometry quantitative measurment water；
In the positive-ion mode, the water sample of the ammonia nitrogen containing known concentration is added to reaction through microsyringe or micro syringe (1)
It in device (2), is reacted with solid alkaline reaction substrate (3) therein, product reaches ion mobility spectrometry (5) through threeway (4) with carrier gas
It is detected, obtains the ion transfer spectrogram of standard specimen；
Unknown concentration sample water is added in reactor (2) through microsyringe or micro syringe (1), with solid therein
Alkaline reaction substrate (3) reaction, product reach ion mobility spectrometry (5) through threeway (4) with carrier gas and are detected, and obtain unknown sample
Ammonia nitrogen ion transfer spectrogram；
The ion transfer spectrogram of the ion transfer spectrogram of standard sample and unknown sample is compared, ammonia nitrogen in unknown sample is obtained
Concentration.
6. according to the method described in claim 5, it is characterized by:
It is added in reactor (2) by the ammonia nitrogen in sample by micro syringe (1), it is anti-with solid alkaline reaction substrate (3)
Product NH should be generated3；Its reaction equation is as follows:
Sample+substrate (3) → NH3↑。
7. according to the method described in claim 5, it is characterized by:
The excessive gas of carrier gas and reactor (2) generation is discharged using threeway (4)；Pass through the first mass flowmenter (6) flow
With the throughput in the flow control ion mobility spectrometry (5) of the second mass flowmenter (7)；By mass flowmenter (7) flow with
The difference of the flow of mass flowmenter (6), the sample size detected needed for extracting ion mobility spectrometry (5) from threeway (4).
8. according to the method described in claim 5, it is characterized by: the electricity in thermostat (11) adds stick (12), through temperature control
Device (15) processed connect with external circuit；Thermostat (11) temperature can maintain a certain particular value in 30 DEG C to 180 DEG C, and usual 50
DEG C to 180 DEG C of a certain particular value.
9. according to the method described in claim 5, it is characterized by: it high throughput can detect the ammonia in water body example at the scene
Nitrogen.
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